U.S. patent application number 11/303925 was filed with the patent office on 2006-07-20 for chemically amplified positive resist composition.
This patent application is currently assigned to Sumitomo Chemical Company, Limited. Invention is credited to Hiromu Sakamoto, Ichiki Takemoto, Satoshi Yamaguchi.
Application Number | 20060160017 11/303925 |
Document ID | / |
Family ID | 36684282 |
Filed Date | 2006-07-20 |
United States Patent
Application |
20060160017 |
Kind Code |
A1 |
Takemoto; Ichiki ; et
al. |
July 20, 2006 |
Chemically amplified positive resist composition
Abstract
The present invention provides a chemically amplified positive
resist composition comprising (i) a polymer which is insoluble or
poorly soluble in an alkali aqueous solution but becomes soluble in
an alkali aqueous solution by the action of an acid, (ii) an acid
generator, and (iii) a compound of the formula (I). ##STR1## The
present invention also provides an ester derivative useful as a
component of the chemically amplified positive resist composition,
and process for producing the ester derivative.
Inventors: |
Takemoto; Ichiki;
(Kawanishi-shi, JP) ; Yamaguchi; Satoshi; (Osaka,
JP) ; Sakamoto; Hiromu; (Osaka, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Sumitomo Chemical Company,
Limited
Tokyo
JP
|
Family ID: |
36684282 |
Appl. No.: |
11/303925 |
Filed: |
December 19, 2005 |
Current U.S.
Class: |
430/270.1 |
Current CPC
Class: |
C07C 69/75 20130101;
G03F 7/0045 20130101; C07C 69/753 20130101; C07C 2602/42 20170501;
C07C 69/75 20130101; C07C 69/753 20130101; C07C 69/75 20130101;
C07C 2601/14 20170501; C07C 67/14 20130101; C07D 493/04 20130101;
C07C 67/11 20130101; C07C 67/11 20130101; G03F 7/0397 20130101;
C07C 67/11 20130101; C07C 67/14 20130101; C07C 2603/74
20170501 |
Class at
Publication: |
430/270.1 |
International
Class: |
G03C 1/76 20060101
G03C001/76 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 22, 2004 |
JP |
2004-370728 |
Claims
1. A chemically amplified positive resist composition comprising
(i) a polymer which is insoluble or poorly soluble in an alkali
aqueous solution but becomes soluble in an alkali aqueous solution
by the action of an acid, (ii) an acid generator, and (iii) a
compound of the formula (I) ##STR50## wherein Z represents
hydrocarbon group having 2 to 14 carbon atom, and at least one of
--CH.sub.2-- except the one bonding to other group adjacent to Z
may be substituted by --O--; A represents divalent alicyclic
hydrocarbon group having 3 to 14 carbon atoms; W represents
hydrogen atom, alkyl group having 1 to 12 carbon atoms, alkoxyalkyl
group having 2 to 12, or a group of the formula (II) ##STR51##
wherein X represents divalent connecting group, R represents
hydrogen atom, alkyl group having 1 to 6 carbon atoms or cycloalkyl
group having 3 to 6 carbon atoms, Y represents atoms necessary to
form an alicyclic hydrocarbon group together with the adjacent
carbon atom and contains 4 to 12 carbon atoms, and at least one of
--CH.sub.2-- in the alicyclic hydrocarbon group may be substituted
by --CO-- or --O--, and at least one of hydrogen atoms in the
alicyclic hydrocarbon group may be substituted by alkyl group
having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon
atoms, trifluoromethyl group, hydroxyl group or cyano group, and I
represents 0 or 1, and each of m and n shows an integer satisfying
the following inequalities. 0.ltoreq.m.ltoreq.13,
1.ltoreq.n.ltoreq.14, 2.ltoreq.m+n.ltoreq.14, and when n is 2 or
more, each of A is the same or the different, and also each of W is
the same or the different.
2. The composition according to claim 1, wherein Z is saturated
acyclic hydrocarbon group having 2 to 14 carbon atoms or saturated
alicyclic hydrocarbon group having 3 to 14 carbon atoms, wherein at
least one of --CH.sub.2-- group except the one bonding to other
group adjacent to Z may be substituted by --O--; A is divalent
saturated alicyclic hydrocarbon group; and X is divalent saturated
acyclic hydrocarbon group or divalent saturated alicyclic
hydrocarbon group, wherein at least one of --CH.sub.2-- in the
hydrocarbon group except the one bonding to other group adjacent to
X may be substituted by --O--, --COO-- or --O--CO--.
3. The composition according to claim 1, wherein the compound of
the formula (I) is a compound of the formula (III) ##STR52##
wherein Z.sup.1 represents a hydrocarbon group having 3 to 6 carbon
atoms, and at least one of --CH.sub.2-- except the one bonding to
other group adjacent to Z.sup.1 may be substituted by --O--;
A.sup.1 represents divalent alicyclic hydrocarbon group having 5 to
10 carbon atoms; W.sup.1 represents hydrogen atom, alkyl group
having 1 to 10 carbon atoms, alkoxyalkyl group having 2 to 6, or a
group of the formula (IV) ##STR53## wherein X.sup.1 represents
methylene group, ethylene group, trimethylene group, tetramethylene
group, or 6-hydroxy-2-norbornanecarboxylic acid
.gamma.-lactone-3,5-diyl group, R.sup.1 represents hydrogen atom,
alkyl group having 1 to 4 carbon atoms or cycloalkyl group having 3
to 6 carbon atoms, Y.sup.1 represents atoms necessary to form an
alicyclic hydrocarbon group together with the adjacent carbon atom
and contains 4 to 10 carbon atoms, and at least one of --CH.sub.2--
in the alicyclic hydrocarbon group may be substituted by --CO-- or
--O--, and at least one of hydrogen atoms in the alicyclic
hydrocarbon group may be substituted by alkyl group having 1 to 6
carbon atoms, alkoxy group having 1 to 6 carbon atoms,
perfluoroalkyl group having 1 to 4 carbon atoms, hydroxyl group or
cyano group, and l.sup.1 represents 0 or 1, and m.sup.1 and n.sup.1
shows an integer satisfying all of the following inequalities.
0.ltoreq.m.sup.1.ltoreq.13, 1.ltoreq.n.sup.1.ltoreq.14,
2.ltoreq.m.sup.1+n.sup.1.ltoreq.14, and when n.sup.1 is 2 or more,
each of A.sup.1 is the same or the different, and each of W.sup.1
is the same or the different.
4. The composition according to claim 3, wherein Z.sup.1 is
saturated acyclic hydrocarbon group having 3 to 6 carbon atoms or
saturated alicyclic hydrocarbon group having 3 to 6 carbon atoms,
wherein at least one of --CH.sub.2-- group except the one bonding
to other group adjacent to Z.sup.1 may be substituted by --O--; and
A.sup.1 is divalent saturated alicyclic hydrocarbon group having 5
to 10 carbon atoms.
5. The composition according to claim 1, wherein the compound of
the formula (I) is a compound of the formula (V) ##STR54## wherein
Z.sup.2 represents a group selected by the following formulae
##STR55## wherein a straight line with an open end shows a bond
which is extended from an adjacent carbon atom and which does not
specifies a group to be bonded, A.sup.2 represents cyclopentylene
group, cyclohexylene group, norbornylene group or adamantylene
group; W.sup.2 represents hydrogen atom, methyl group, ethyl group,
isopropyl group, butyl group, methoxymethyl group, ethoxymethyl
group, propoxymethyl group, methoxyethyl group, ethoxyethyl group,
or a group of the formula (VI) ##STR56## wherein X.sup.2 represents
methylene group or ethylene group, R.sup.2 represents hydrogen
atom, methyl group, ethyl group, isopropyl group, butyl group,
cyclopentyl group or cyclohexyl group, Y.sup.2 represents atoms
necessary to form cyclopentyl group, cyclohexyl group, norbornyl
group or adamantyl group together with the adjacent carbon atom,
and at least one of --CH.sub.2-- in the cyclopentyl group,
cyclohexyl group, norbornyl group or adamantyl group may be
substituted by --CO-- or --O--, and at least one of hydrogen atoms
in the cyclopentyl group, cyclohexyl group, norbornyl group or
adamantyl group may be substituted by methyl group, ethyl group,
isopropyl group, butyl group, methoxy group, ethoxy group, propoxy
group trifluoromethyl group, hydroxyl group or cyano group, and 12
represents 0 or 1, and m.sup.2 and n.sup.2 shows an integer
satisfying all of the following inequalities.
0.ltoreq.m.sup.2.ltoreq.4, 1.ltoreq.n.sup.2.ltoreq.5,
2.ltoreq.m.sup.2+n.sup.2.ltoreq.5, and when n.sup.2 is 2 or more,
each of A.sup.2 is the same or the different, and also each of
W.sup.2 is the same or the different.
6. An ester derivative of the formula (VII) ##STR57## wherein
Z.sup.3 represents hydrocarbon group having 2 to 14 carbon atom,
and at least one of --CH.sub.2-- except the one bonding to other
group adjacent to Z.sup.3 may be substituted by --O--; A.sup.3
represents divalent alicyclic hydrocarbon group having 3 to 14
carbon atoms; W.sup.3 represents hydrogen atom, alkyl group having
1 to 12 carbon atoms or a group of the formula (VIII) ##STR58##
wherein X.sup.3 represents divalent connecting group, R.sup.3
represents hydrogen atom, alkyl group having 1 to 6 carbon atoms or
cycloalkyl group having 3 to 6 carbon atoms, Y.sup.3 represents
atoms necessary to form an alicyclic hydrocarbon group together
with the adjacent carbon atom and contains 3 to 12 carbon atoms,
and at least one of --CH.sub.2-- in the alicyclic hydrocarbon group
may be substituted by --CO-- or --O--, and at least one of hydrogen
atoms in the alicyclic hydrocarbon group may be substituted by
alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6
carbon atoms, perfluoroalkyl group having 1 to 4 carbon atoms,
hydroxyl group or cyano group, and 1.sup.3 represents 0 or 1, and
m.sup.3 and n.sup.3 show an integer satisfying all of the following
inequalities, 0.ltoreq.m.sup.3.ltoreq.13,
1.ltoreq.n.sup.3.ltoreq.14, 2.ltoreq.m.sup.3+n.sup.3.ltoreq.14, and
when n.sup.3 is 2 or more, each of A.sup.3 is the same or the
different, and also each of W.sup.3 is the same or the
different.
7. The ester derivative according to claim 6, wherein Z.sup.3 is
saturated acyclic hydrocarbon group having 2 to 14 carbon atoms or
saturated alicyclic hydrocarbon group having 3 to 14 carbon atoms,
wherein at least one of --CH.sub.2-- group except the one bonding
to other group adjacent to Z.sup.3 may be substituted by --O--;
A.sup.3 is divalent saturated alicyclic hydrocarbon group; and
X.sup.3 is divalent saturated acyclic hydrocarbon group or divalent
saturated alicyclic hydrocarbon group, wherein at least one of
--CH.sub.2-- in the hydrocarbon group except the one bonding to
other group adjacent to X.sup.3 may be substituted by --O--,
--COO-- or --O--CO--.
8. A process for producing a compound of the formula (VII')
##STR59## wherein Z.sup.4 represents hydrocarbon group having 2 to
14 carbon atom, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.4 may be substituted by
--O--; A.sup.4 represents divalent alicyclic hydrocarbon group
having 3 to 14 carbon atoms; R.sup.4 represents hydrogen atom,
alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3
to 6 carbon atoms, Y.sup.4 represents atoms necessary to form an
alicyclic hydrocarbon group together with the adjacent carbon atom
and contains 3 to 12 carbon atoms, and at least one of --CH.sub.2--
in the alicyclic hydrocarbon group may be substituted by --CO-- or
--O--, and at least one of hydrogen atoms in the alicyclic
hydrocarbon group may be substituted by alkyl group having 1 to 6
carbon atoms, alkoxy group having 1 to 6 carbon atoms,
perfluoroalkyl group having 1 to 4 carbon atoms, hydroxyl group or
cyano group, and each of m.sup.4 and n.sup.4 shows an integer
satisfying the following inequalities. 0.ltoreq.m.sup.4.ltoreq.13,
1.ltoreq.n.sup.414, 2.ltoreq.m.sup.4+n.sup.4.ltoreq.14, and when
n.sup.4 is 2 or more, each of A.sup.4 is the same or the different,
each of R.sup.4 is the same or the different, and each of alicyclic
hydrocarbon group formed by Y.sup.4 and the carbon atom adjacent to
Y.sup.4 is the same or different, which comprises a step comprising
reacting a compound of the formula (IX) ##STR60## wherein Q
represents chlorine atom, bromine atom, iodine atom or imidazolyl
group, G.sup.4 represents a group protecting hydroxyl group, and
Z.sup.4, A.sup.4, m.sup.4 and n.sup.4 have the same meanings as
defined above, with an alcohol derivative of the formula (X)
##STR61## wherein R.sup.4 and Y.sup.4 have the same meanings as
defined above, in the presence of deacidifying agent, and a step
subjecting the reaction product obtained by the step above to
deprotection.
9. The process according to claim 8, wherein Z.sup.4 is saturated
acyclic hydrocarbon group having 2 to 14 carbon atoms or saturated
alicyclic hydrocarbon group having 3 to 14 carbon atoms, wherein at
least one of --CH.sub.2-- group except the one bonding to other
group adjacent to Z.sup.4 may be substituted by --O--; and G.sup.4
is trialkylsilyl group.
10. A process for producing a compound of the formula (VII'')
##STR62## wherein Z.sup.5 represents hydrocarbon group having 2 to
14 carbon atom, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.5 may be substituted by
--O--; A.sup.5 represents divalent alicyclic hydrocarbon group
having 3 to 14 carbon atoms; X.sup.5 represents divalent connecting
group; R.sup.5 represents hydrogen atom, alkyl group having 1 to 6
carbon atoms or cycloalkyl group having 3 to 6 carbon atoms,
Y.sup.5 represents atoms necessary to form an alicyclic hydrocarbon
group together with the adjacent carbon atom and contains 3 to 12
carbon atoms, and at least one of --CH.sub.2-- in the alicyclic
hydrocarbon group may be substituted by --CO-- or --O--, and at
least one of hydrogen atoms in the alicyclic hydrocarbon group may
be substituted by alkyl group having 1 to 6 carbon atoms, alkoxy
group having 1 to 6 carbon atoms, perfluoroalkyl group having 1 to
4 carbon atoms, hydroxyl group or cyano group, and each of m.sup.5
and n.sup.5 shows an integer satisfying the following inequalities.
0.ltoreq.m.sup.5.ltoreq.13, 1.ltoreq.n.sup.5.ltoreq.14,
2.ltoreq.m.sup.5+n.sup.5.ltoreq.14, and when n.sup.5 is 2 or more,
each of A.sup.5 is the same or the different, each of R.sup.5 is
the same or the different, each of X.sup.5 is the same or the
different, and each of alicyclic hydrocarbon group formed by
Y.sup.5 and the carbon atom adjacent to Y.sup.5 is the same or
different, which comprises reacting a compound of the formula (XI)
##STR63## wherein G.sup.5 represents hydrogen atom or a group
protecting hydroxyl group, and Z.sup.5, A.sup.5, m.sup.5 and
n.sup.5 have the same meanings as defined above, with a compound of
the formula (XII) ##STR64## wherein Q.sup.5 represents chlorine
atom, bromine atom or iodine atom, X.sup.5, R.sup.5 and Y.sup.5
have the same meanings as defined above, in the presence of
deacidifying agent, and further comprises subjecting the reaction
product obtained by the reaction of the compounds (XI) and (XII)
above to deprotection when G.sup.5 is the group protecting hydroxyl
group.
11. The composition according to claim 10, wherein Z.sup.5 is
saturated acyclic hydrocarbon group having 2 to 14 carbon atoms or
saturated alicyclic hydrocarbon group having 3 to 14 carbon atoms,
wherein at least one of --CH.sub.2-- group except the one bonding
to other group adjacent to Z.sup.5 may be substituted by --O--;
A.sup.5 is divalent saturated alicyclic hydrocarbon group; and
X.sup.5 is divalent saturated acyclic hydrocarbon group or divalent
saturated alicyclic hydrocarbon group, wherein at least one of
--CH.sub.2-- in the hydrocarbon group except the one bonding to
other group adjacent to X.sup.5 may be substituted by --O--,
--COO-- or --O--CO--.
Description
[0001] This nonprovisional application claims priority under 35
U.S.C. .sctn. 119(a) on Patent Application No. 2004-370728 filed in
JAPAN on Dec. 22, 2004, the entire contents of which are hereby
incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a chemically amplified
positive resist composition for use in micro fabrication of
semiconductor, a supramolecule useful for a component of the resist
composition, and a process for producing thereof.
BACKGROUND OF THE INVENTION
[0003] Semiconductor microfabrication employs a lithography process
using a resist composition. In lithography, theoretically, the
shorter the exposure wavelength becomes, the higher the resolution
can be made, as expressed by Rayleigh's diffraction limit formula.
The wavelength of an exposure light source for lithography used in
the manufacture of semiconductor devices has been shortened year by
year as g line having a wavelength of 436 nm, i line having a
wavelength of 365 nm, KrF excimer laser having a wavelength of 248
nm and ArF excimer laser having a wavelength of 193 nm. Further, as
the exposure light source of the subsequent generation, soft X ray
(EUV) having a wavelength of 13 nm or shorter has been proposed as
the exposure light source.
[0004] As line width has become narrower in lithography process
using light sources having shorter wavelength, such as excimer
laser and the like, especially line edge roughness (roughness of
pattern surfaces or wave of pattern, abbreviated by LER), as well
as resolution, sensitivity and pattern shape, has become important
subject (e.g. Proc. of SPIE Vol. 5038 (2003), 689-698).
[0005] With further advance of microfabrication technology, it is
required for new photoresist compositions to show more advantageous
abilities than conventional photoresists. Specifically, photoresist
compositions giving better resolution, sensitivity, pattern
profiles to resist pattern obtained therefrom, especially giving
better line edge roughness are required.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide a
chemically amplified resist composition suitable for ArF excimer
laser lithography, showing excellent various resist abilities such
as resolution, sensitivity, pattern shape and the like, and giving
particularly excellent line edge roughness.
[0007] Another object of the present invention is to provide a
supramolecule useful for a component of a photoresist
composition.
[0008] Still another object of the present invention is to provide
a process for producing the supramolecule.
[0009] These and other objects of the present invention will be
apparent from the following description.
[0010] The present invention relates to the followings:
<1> A chemically amplified positive resist composition
comprising
(i) a polymer which is insoluble or poorly soluble in an alkali
aqueous solution but becomes soluble in an alkali aqueous solution
by the action of an acid,
(ii) an acid generator, and
[0011] (iii) a compound of the formula (I) ##STR2##
[0012] wherein Z represents hydrocarbon group having 2 to 14 carbon
atom, and at least one of --CH.sub.2-- except the one bonding to
other group adjacent to Z may be substituted by --O--; A represents
divalent alicyclic hydrocarbon group having 3 to 14 carbon atoms; W
represents hydrogen atom, alkyl group having 1 to 12 carbon atoms,
alkoxyalkyl group having 2 to 12, or a group of the formula (II)
##STR3##
[0013] wherein X represents divalent connecting group, R represents
hydrogen atom, alkyl group having 1 to 6 carbon atoms or cycloalkyl
group having 3 to 6 carbon atoms, Y represents atoms necessary to
form an alicyclic hydrocarbon group together with the adjacent
carbon atom and contains 4 to 12 carbon atoms, and at least one of
--CH.sub.2-- in the alicyclic hydrocarbon group may be substituted
by --CO-- or --O--, and at least one of hydrogen atoms in the
alicyclic hydrocarbon group may be substituted by alkyl group
having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon
atoms, trifluoromethyl group, hydroxyl group or cyano group, and 1
represents 0 or 1, and
[0014] each of m and n shows an integer satisfying the following
inequalities. 0.ltoreq.m.ltoreq.13, 1.ltoreq.n.ltoreq.14,
2.ltoreq.m+n.ltoreq.14, and
[0015] when n is 2 or more, each of A is the same or the different,
and also each of W is the same or the different.
[0016] <2> The composition according to <1>, wherein Z
is saturated acyclic hydrocarbon group having 2 to 14 carbon atoms
or saturated alicyclic hydrocarbon group having 3 to 14 carbon
atoms, wherein at least one of --CH.sub.2-- group except the one
bonding to other group adjacent to Z may be substituted by --O--; A
is divalent saturated alicyclic hydrocarbon group; and X is
divalent saturated acyclic hydrocarbon group or divalent saturated
alicyclic hydrocarbon group, wherein at least one of --CH.sub.2--
in the hydrocarbon group except the one bonding to other group
adjacent to X may be substituted by --O--, --COO-- or --O--CO--.
<3> The composition according to <1>, wherein the
compound of the formula (I) is a compound of the formula (III)
##STR4##
[0017] wherein Z.sup.1 represents a hydrocarbon group having 3 to 6
carbon atoms, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.1 may be substituted by
--O--; A.sup.1 represents divalent alicyclic hydrocarbon group
having 5 to 10 carbon atoms; W.sup.1 represents hydrogen atom,
alkyl group having 1 to 10 carbon atoms, alkoxyalkyl group having 2
to 6, or a group of the formula (IV) ##STR5##
[0018] wherein X.sup.1 represents methylene group, ethylene group,
trimethylene group, tetramethylene group, or
6-hydroxy-2-norbornanecarboxylic acid .gamma.-lactone-3,5-diyl
group, R.sup.1 represents hydrogen atom, alkyl group having 1 to 4
carbon atoms or cycloalkyl group having 3 to 6 carbon atoms,
Y.sup.1 represents atoms necessary to form an alicyclic hydrocarbon
group together with the adjacent carbon atom and contains 4 to 10
carbon atoms, and at least one of --CH.sub.2-- in the alicyclic
hydrocarbon group may be substituted by --CO-- or --O--, and at
least one of hydrogen atoms in the alicyclic hydrocarbon group may
be substituted by alkyl group having 1 to 6 carbon atoms, alkoxy
group having 1 to 6 carbon atoms, perfluoroalkyl group having 1 to
4 carbon atoms, hydroxyl group or cyano group, and .sup.1
represents 0 or 1, and
[0019] m.sup.1 and n.sup.1 shows an integer satisfying all of the
following inequalities. 0.ltoreq.m.sup.1<13,
1.ltoreq.n.sup.1.ltoreq.14, 2.ltoreq.m.sup.1+n.sup.1.ltoreq.14, and
when n.sup.1 is 2 or more, each of A.sup.1 is the same or the
different, and each of W.sup.1 is the same or the different.
<4> The composition according to <3>, wherein Z.sup.1
is saturated acyclic hydrocarbon group having 3 to 6 carbon atoms
or saturated alicyclic hydrocarbon group having 3 to 6 carbon
atoms, wherein at least one of --CH.sub.2-- group except the one
bonding to other group adjacent to Z.sup.1 may be substituted by
--O--; and A.sup.1 is divalent saturated alicyclic hydrocarbon
group having 5 to 10 carbon atoms. <5> The composition
according to <1>, wherein the compound of the formula (I) is
a compound of the formula (V) ##STR6##
[0020] wherein Z.sup.2 represents a group selected by the following
formulae ##STR7##
[0021] wherein a straight line with an open end shows a bond which
is extended from an adjacent carbon atom and which does not
specifies a group to be bonded, A.sup.2 represents cyclopentylene
group, cyclohexylene group, norbornylene group or adamantylene
group; W.sup.2 represents hydrogen atom, methyl group, ethyl group,
isopropyl group, butyl group, methoxymethyl group, ethoxymethyl
group, propoxymethyl group, methoxyethyl group, ethoxyethyl group,
or a group of the formula (VI) ##STR8##
[0022] wherein X.sup.2 represents methylene group or ethylene
group, R.sup.2 represents hydrogen atom, methyl group, ethyl group,
isopropyl group, butyl group, cyclopentyl group or cyclohexyl
group, Y.sup.2 represents atoms necessary to form cyclopentyl
group, cyclohexyl group, norbornyl group or adamantyl group
together with the adjacent carbon atom, and at least one of
--CH.sub.2-- in the cyclopentyl group, cyclohexyl group, norbornyl
group or adamantyl group may be substituted by --CO-- or --O--, and
at least one of hydrogen atoms in the cyclopentyl group, cyclohexyl
group, norbornyl group or adamantyl group may be substituted by
methyl group, ethyl group, isopropyl group, butyl group, methoxy
group, ethoxy group, propoxy group trifluoromethyl group, hydroxyl
group or cyano group, and l.sup.2 represents 0 or 1, and
[0023] m.sup.2 and n.sup.2 shows an integer satisfying all of the
following inequalities. 0.ltoreq.m.sup.2.ltoreq.4,
1.ltoreq.n.sup.2.ltoreq.5, 2.ltoreq.m.sup.2+n.sup.2.ltoreq.5
and
[0024] when n.sup.2 is 2 or more, each of A.sup.2 is the same or
the different, and also each of W.sup.2 is the same or the
different. <6> An ester derivative of the formula (VII)
##STR9##
[0025] wherein Z.sup.3 represents hydrocarbon group having 2 to 14
carbon atom, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.3 may be substituted by
--O--; A.sup.3 represents divalent alicyclic hydrocarbon group
having 3 to 14 carbon atoms; W.sup.3 represents hydrogen atom,
alkyl group having 1 to 12 carbon atoms or a group of the formula
(VIII) ##STR10##
[0026] wherein X.sup.3 represents divalent connecting group,
R.sup.3 represents hydrogen atom, alkyl group having 1 to 6 carbon
atoms or cycloalkyl group having 3 to 6 carbon atoms, Y.sup.3
represents atoms necessary to form an alicyclic hydrocarbon group
together with the adjacent carbon atom and contains 3 to 12 carbon
atoms, and at least one of --CH.sub.2-- in the alicyclic
hydrocarbon group may be substituted by --CO-- or --O--, and at
least one of hydrogen atoms in the alicyclic hydrocarbon group may
be substituted by alkyl group having 1 to 6 carbon atoms, alkoxy
group having 1 to 6 carbon atoms, perfluoroalkyl group having 1 to
4 carbon atoms, hydroxyl group or cyano group, and l.sup.3
represents 0 or 1, and
[0027] m.sup.3 and n.sup.3 show an integer satisfying all of the
following inequalities, 0.ltoreq.m.sup.3.ltoreq.13,
1.ltoreq.n.sup.3.ltoreq.14, 2.ltoreq.m.sup.3+n.sup.3.ltoreq.14,
and
[0028] when n.sup.3 is 2 or more, each of A.sup.3 is the same or
the different, and also each of W.sup.3 is the same or the
different.
[0029] <7> The ester derivative according to <6>,
wherein Z.sup.3 is saturated acyclic hydrocarbon group having 2 to
14 carbon atoms or saturated alicyclic hydrocarbon group having 3
to 14 carbon atoms, wherein at least one of --CH.sub.2-- group
except the one bonding to other group adjacent to Z.sup.3 may be
substituted by --O--; A.sup.3 is divalent saturated alicyclic
hydrocarbon group; and X.sup.3 is divalent saturated acyclic
hydrocarbon group or divalent saturated alicyclic hydrocarbon
group, wherein at least one of --CH.sub.2-- in the hydrocarbon
group except the one bonding to other group adjacent to X.sup.3 may
be substituted by --O--, --COO-- or --O--CO--. <8> A process
for producing a compound of the formula (VII') ##STR11##
[0030] wherein Z.sup.4 represents hydrocarbon group having 2 to 14
carbon atom, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.4 may be substituted by
--O--; A.sup.4 represents divalent alicyclic hydrocarbon group
having 3 to 14 carbon atoms; R.sup.4 represents hydrogen atom,
alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3
to 6 carbon atoms, Y.sup.4 represents atoms necessary to form an
alicyclic hydrocarbon group together with the adjacent carbon atom
and contains 3 to 12 carbon atoms, and at least one of --CH.sub.2--
in the alicyclic hydrocarbon group may be substituted by --CO-- or
--O--, and at least one of hydrogen atoms in the alicyclic
hydrocarbon group may be substituted by alkyl group having 1 to 6
carbon atoms, alkoxy group having 1 to 6 carbon atoms,
perfluoroalkyl group having 1 to 4 carbon atoms, hydroxyl group or
cyano group, and
[0031] each of m.sup.4 and n.sup.4 shows an integer satisfying the
following inequalities. 0.ltoreq.m.sup.4.ltoreq.13,
1.ltoreq.n.sup.4.ltoreq.14, 2.ltoreq.m.sup.4+n.sup.4.ltoreq.14,
and
[0032] when n.sup.4 is 2 or more, each of A.sup.4 is the same or
the different, each of R.sup.4 is the same or the different, and
each of alicyclic hydrocarbon group formed by Y.sup.4 and the
carbon atom adjacent to Y.sup.4 is the same or different, which
comprises a step comprising reacting a compound of the formula (IX)
##STR12##
[0033] wherein Q represents chlorine atom, bromine atom, iodine
atom or imidazolyl group, G.sup.4 represents a group protecting
hydroxyl group, and Z.sup.4, A.sup.4, m.sup.4 and n.sup.4 have the
same meanings as defined above, with an alcohol derivative of the
formula (X) ##STR13##
[0034] wherein R.sup.4 and Y.sup.4 have the same meanings as
defined above,
in the presence of deacidifying agent, and
a step subjecting the reaction product obtained by the step above
to deprotection.
[0035] <9> The process according to <8>, wherein
Z.sup.4 is saturated acyclic hydrocarbon group having 2 to 14
carbon atoms or saturated alicyclic hydrocarbon group having 3 to
14 carbon atoms, wherein at least one of --CH.sub.2-- group except
the one bonding to other group adjacent to Z.sup.4 may be
substituted by --O--; and G.sup.4 is trialkylsilyl group.
<10> A process for producing a compound of the formula
(VII'') ##STR14##
[0036] wherein Z.sup.5 represents hydrocarbon group having 2 to 14
carbon atom, and at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.5 may be substituted by
--O--; A.sup.5 represents divalent alicyclic hydrocarbon group
having 3 to 14 carbon atoms; X.sup.5 represents divalent connecting
group; R.sup.5 represents hydrogen atom, alkyl group having 1 to 6
carbon atoms or cycloalkyl group having 3 to 6 carbon atoms,
Y.sup.5 represents atoms necessary to form an alicyclic hydrocarbon
group together with the adjacent carbon atom and contains 3 to 12
carbon atoms, and at least one of --CH.sub.2-- in the alicyclic
hydrocarbon group may be substituted by --CO-- or --O--, and at
least one of hydrogen atoms in the alicyclic hydrocarbon group may
be substituted by alkyl group having 1 to 6 carbon atoms, alkoxy
group having 1 to 6 carbon atoms, perfluoroalkyl group having 1 to
4 carbon atoms, hydroxyl group or cyano group, and
[0037] each of m.sup.5 and n.sup.5 shows an integer satisfying the
following inequalities. 0.ltoreq.m.sup.5.ltoreq.13,
1.ltoreq.n.sup.5.ltoreq.14, 2.ltoreq.m.sup.5+n.sup.5.ltoreq.14,
and
[0038] when n.sup.5 is 2 or more, each of A.sup.5 is the same or
the different, each of R.sup.5 is the same or the different, each
of X.sup.5 is the same or the different, and each of alicyclic
hydrocarbon group formed by Y.sup.5 and the carbon atom adjacent to
Y.sup.5 is the same or different, which comprises reacting a
compound of the formula (XI) ##STR15##
[0039] wherein G.sup.5 represents hydrogen atom or a group
protecting hydroxyl group, and Z.sup.5, A.sup.5, m.sup.5 and
n.sup.5 have the same meanings as defined above, with a compound of
the formula (XII) ##STR16##
[0040] wherein Q.sup.5 represents chlorine atom, bromine atom or
iodine atom, X.sup.5, R.sup.5 and Y.sup.5 have the same meanings as
defined above,
in the presence of deacidifying agent, and
further comprises subjecting the reaction product obtained by the
reaction of the compounds (XI) and (XII) above to deprotection when
G.sup.5 is the group protecting hydroxyl group.
[0041] <11> The composition according to <10>, wherein
Z.sup.5 is saturated acyclic hydrocarbon group having 2 to 14
carbon atoms or saturated alicyclic hydrocarbon group having 3 to
14 carbon atoms, wherein at least one of --CH.sub.2-- group except
the one bonding to other group adjacent to Z.sup.5 may be
substituted by --O--; A.sup.5 is divalent saturated alicyclic
hydrocarbon group; and X.sup.5 is divalent saturated acyclic
hydrocarbon group or divalent saturated alicyclic hydrocarbon
group, wherein at least one of --CH.sub.2-- in the hydrocarbon
group except the one bonding to other group adjacent to X.sup.5 may
be substituted by --O--, --COO-- or --O--CO--.
[0042] Hereinafter, "compound of the formula (I)", "compound of the
formula (III)", "compound of the formula (V)", "ester derivative of
the formula (VII)", "ester derivative of the formula (VII')",
"ester derivative of the formula (VII'')", "compound of the formula
(IX)", "alcohol derivative of the formula (X)", "compound of the
formula (XI)" and "compound of the formula (XII)" may be referred
to as "Supracompound (I)", "Supracompound (III)", "Supracompound
(V)", "Ester Derivative (VII)", "Ester Derivative (VII')", "Ester
Derivative (VII'')", "Compound (IX)", "Alcohol Derivative (X)",
"Compound (XI)" and "Compound (XII)", respectively.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0043] The present composition useful for a chemically amplified
photoresist comprises
(i) a polymer which is insoluble or poorly soluble in an alkali
aqueous solution but becomes soluble in an alkali aqueous solution
by the action of an acid, (ii) an acid generator, and (iii)
Supracompound (I).
[0044] In Supracompound (I), Z represents hydrocarbon group having
2 to 14 carbon atom, preferably saturated acyclic hydrocarbon group
having 2 to 14 carbon atoms and saturated alicyclic hydrocarbon
group having 3 to 14 carbon atoms, more preferably saturated
acyclic hydrocarbon group having 3 to 6 carbon atoms and saturated
alicyclic hydrocarbon group having 3 to 6 carbon atoms. And at
least one of --CH.sub.2-- except the one bonding to other group
adjacent to Z may be substituted by --O--. A represents divalent
alicyclic hydrocarbon group having 3 to 14 carbon atoms, preferably
3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. W
represents hydrogen atom, alkyl group having 1 to 12 carbon atoms,
alkoxyalkyl group having 2 to 12, or a group of the formula (II),
preferably hydrogen atom, alkyl group having 1 to 10 carbon atoms,
alkoxyalkyl group having 2 to 6, or a group of the formula (IV),
more preferably hydrogen atom, ethyl group, isopropyl group butyl
group, methoxymethyl group, ethoxymethyl group, propoxymethyl
group, methoxyethyl group, ethoxyethyl group or a group of the
formula (VI).
[0045] X in the group of the formula (II) represents divalent
connecting group; preferably divalent saturated acyclic hydrocarbon
group or divalent saturated alicyclic hydrocarbon group, wherein at
least one of --CH.sub.2-- in the saturated acyclic or alicyclic
hydrocarbon group except the one bonding to other group adjacent to
X may be substituted by --O--, --COO-- or --OCO--; more preferably
methylene group, ethylene group, trimethylene group or
tetramethylene group; more preferably methylene group or ethylene
group. Y in the group of the formula (II) represents atoms
necessary to form an alicyclic hydrocarbon group together with the
adjacent carbon atom and contains 4 to 12, preferably 4 to 10
carbon atoms; more preferably atoms necessary to form cyclopentyl
group, cyclohexyl group, norbornyl group or adamantyl group
together with the adjacent carbon atom. R represents hydrogen atom,
alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3
to 6 carbon atoms, preferably hydrogen atom, alkyl group having 1
to 4 carbon atoms or cycloalkyl group having 3 to 6 carbon atoms,
more preferably hydrogen atom, methyl group, ethyl group, isopropyl
group, butyl group, cyclopentyl group or cyclohexyl group. Each of
m and n in the formula (I) shows an integer satisfying the
inequalities of 0.ltoreq.m.ltoreq.13, 1.ltoreq.n.ltoreq.14 and
2.ltoreq.m+n.ltoreq.14, and preferably of 0.ltoreq.m.ltoreq.4,
1.ltoreq.n.ltoreq.5 and 2.ltoreq.m+n.ltoreq.5. l represents 0 or
1.
[0046] In Ester Derivative (VII), Ester Derivative (VII') and Ester
Derivative (VII''), each of Z.sup.3, Z.sup.4 and Z.sup.5 represents
hydrocarbon group having 2 to 14 carbon atom, preferably saturated
acyclic hydrocarbon group having 2 to 14 carbon atoms and saturated
alicyclic hydrocarbon group having 3 to 14 carbon atoms, more
preferably saturated acyclic hydrocarbon group having 3 to 6 carbon
atoms and saturated alicyclic hydrocarbon group having 3 to 6
carbon atoms. And at least one of --CH.sub.2-- except the one
bonding to other group adjacent to Z.sup.3, Z.sup.4 or Z.sup.5 may
be substituted by --O--. Each of A.sup.3, A.sup.4 and A.sup.5
represents divalent alicyclic hydrocarbon group having 3 to 14
carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to
8 carbon atoms. W.sup.3 represents hydrogen atom, alkyl group
having 1 to 12 carbon atoms, alkoxyalkyl group having 2 to 12, or a
group of the formula (VIII), preferably hydrogen atom, alkyl group
having 1 to 10 carbon atoms, alkoxyalkyl group having 2 to 6, or a
group of the formula (IV), more preferably hydrogen atom, ethyl
group, isopropyl group butyl group, methoxymethyl group,
ethoxymethyl group, propoxymethyl group, methoxyethyl group,
ethoxyethyl group or a group of the formula (VI).
[0047] In the group of the formula (VIII) and Ester Derivative
(VII''), each of X.sup.3 and X.sup.5 represents divalent connecting
group; preferably divalent saturated acyclic hydrocarbon group or
divalent saturated alicyclic hydrocarbon group, wherein at least
one of --CH.sub.2-- in the saturated acyclic or alicyclic
hydrocarbon group except the one bonding to other group adjacent to
X.sup.3 or X.sup.5 may be substituted by --O--, --COO-- or --OCO--;
more preferably methylene group, ethylene group, trimethylene group
or tetramethylene group; more preferably methylene group or
ethylene group. In the group of the formula (VIII), Ester
Derivative (VII') and Ester Derivative (VII''), each of Y.sup.3,
Y.sup.4 and Y.sup.5 represents atoms necessary to form an alicyclic
hydrocarbon group together with the adjacent carbon atom and
contains 4 to 12, preferably 4 to 10 carbon atoms; more preferably
atoms necessary to form cyclopentyl group, cyclohexyl group,
norbornyl group or adamantyl group together with the adjacent
carbon atom. Each of R.sup.3, R.sup.4 and R.sup.5 represents
hydrogen atom, alkyl group having 1 to 6 carbon atoms or cycloalkyl
group having 3 to 6 carbon atoms, preferably hydrogen atom, alkyl
group having 1 to 4 carbon atoms or cycloalkyl group having 3 to 6
carbon atoms, more preferably hydrogen atom, methyl group, ethyl
group, isopropyl group, butyl group, cyclopentyl group or
cyclohexyl group.
[0048] Each of m.sup.3 and n.sup.3 in the formula (VII) shows an
integer satisfying the inequalities of 0.ltoreq.m.sup.3.ltoreq.13,
1.ltoreq.n.sup.3.ltoreq.14 and 2.ltoreq.m.sup.3+n.sup.3.ltoreq.14,
and preferably of 0.ltoreq.m.sup.3.ltoreq.4,
1.ltoreq.n.sup.3.ltoreq.5 and 2.ltoreq.m.sup.3+n.sup.3.ltoreq.5.
l.sup.3 represents 0 or 1.
[0049] Each of m.sup.4 and n.sup.4 in the formula (VII') shows an
integer satisfying the inequalities of 0.ltoreq.m.sup.4.ltoreq.13,
1.ltoreq.n.sup.4.ltoreq.14 and 2.ltoreq.m.sup.4+n.sup.4.ltoreq.14,
and preferably of 0.ltoreq.m.sup.4.ltoreq.4,
1.ltoreq.n.sup.4.ltoreq.5 and
2.ltoreq.m.sup.4+n.sup.4.ltoreq.5.
[0050] Each of m.sup.5 and n.sup.5 in the formula (VII'') shows an
integer satisfying the inequalities of 0.ltoreq.m.sup.5.ltoreq.13,
1.ltoreq.n.sup.5.ltoreq.14 and 2.ltoreq.m.sup.5+n.sup.5.ltoreq.14,
and preferably of 0.ltoreq.m.sup.5.ltoreq.4,
1.ltoreq.n.sup.5.ltoreq.5 and
2.ltoreq.m.sup.5+n.sup.5.ltoreq.5.
[0051] Q.sup.5 in Compound (IX) represents chlorine atom, bromine
atom, iodine atom or imidazolyl group, and Q.sup.5 in Compound
(XII) represents chlorine atom, bromine atom or iodine atom.
[0052] G.sup.4 in Compound (IX) represents protecting group of
hydroxyl group, and preferable examples include trialkylsilyl group
such as trimethylsilyl group, allyl group, benzyl group,
tetrahydropyranyl group, and the like. G.sup.5 in Compound (XI)
represents hydrogen atom or a protecting group of hydroxyl group,
and preferable examples of the protecting group include
trialkylsilyl group such as trimethylsilyl group, allyl group,
benzyl group, tetrahydropyranyl group, and the like.
[0053] Specific examples of Z, Z.sup.3, Z.sup.4 and Z.sup.5 include
the groups of the following formulae: ##STR17## In each of the
formulae above, a straight line with an open end shows a bond which
is extended from an adjacent carbon atom and which does not
specifies a group to be bonded.
[0054] Specific examples of A, A.sup.3, A.sup.4 and A.sup.5 include
the groups of the following formulae: ##STR18## In each of the
formulae above, a straight line with an open end shows a bond which
is extended from an adjacent carbon atom and which does not
specifies a group to be bonded.
[0055] Specific examples of W and W.sup.3 include the groups of the
following formulae: ##STR19## ##STR20##
[0056] In each of the formulae above, a straight line with an open
end shows a bond which is extended from an adjacent carbon atom and
which does not specifies a group to be bonded. Specific examples of
the groups of the formulae ##STR21## include the following
formulae: ##STR22## ##STR23## ##STR24## ##STR25## ##STR26##
##STR27##
[0057] In each of the formulae above, a straight line with an open
end shows a bond which is extended from an adjacent carbon atom and
which does not specifies a group to be bonded.
[0058] Specific examples of X, X.sup.3 and X.sup.5 include the
groups of the following formulae: ##STR28##
[0059] In each of the formulae above, a straight line with an open
end shows a bond which is extended from an adjacent carbon atom and
which does not specifies a group to be bonded.
[0060] Preferred examples of Supracompound (I) include
Supracompound (III) and more preferred examples include
Supracompound (V).
[0061] Ester Derivative (VII) can be obtained by reacting ester
derivative with alcohol derivative in the presence of deacidifying
agent, and then deprotecting the reaction product.
[0062] For example, Ester Derivative (VII') can be obtained by
reacting Compound (IX) with Alcohol Derivative (X) in the presence
of deacidifying agent, and subjecting the reaction product obtained
by the reaction above to deprotection. The amount of Alcohol
Derivative (X) is usually 1 to 2 gram equivalents, preferably 1 to
1.5 gram equivalents, per 1 gram equivalent of Compound (IX). The
amount of deacidifying agent is usually 1 to 5 gram equivalents,
preferably 1 to 3 gram equivalents, per 1 gram equivalent of
Compound (IX).
[0063] The reaction of Compound (IX) with Alcohol Derivative (X) is
usually conducted in an inert solvent such as toluene,
tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and the
like. Examples of the deacidifying agent include organic base such
as amines (e.g. triethylamine, etc.), pyridines (e.g. pyridine,
picoline, etc.), and the like, inorganic base such as alkali metal
hydroxide (e.g. sodium hydroxide, potassium hydroxide, etc.),
alkali metal carbonate (e.g. potassium carbonate, sodium carbonate,
etc.), and a mixture thereof.
[0064] The reaction can be conducted, for example, by a method of
adding a deacidifying agent into a solution of Compound (IX) and
Alcohol Derivative (X) in a solvent. Alternatively it can also be
conducted by a method of adding Compound (IX) into a solution of
Alcohol Derivative (X) and deacidifying agent in a solvent.
[0065] The reaction temperature is usually -30 to +200.degree. C.,
preferably 0 to 150.degree. C. The reaction can be conducted in the
presence of phase transfer catalysts such as tetrabutylammonium
bromide.
[0066] After the reaction, the product can be isolated by
conducting conventional method such as neutralization, extraction,
crystallization, condensation, and the like. Further, the product
can be purified, for example, by recrystallization, chromatography,
and the like.
[0067] The deprotection reaction can be conducted in a conventional
manner. For example, when the protecting group of hydroxyl group is
trimethylsilyl group, it can be performed by using desilylating
agent such as tetrabutylammonium fluoride. The amount of the
desilylating agent is usually 1 to 10 gram equivalents, preferably
1 to 2 gram equivalents, per 1 gram equivalent of the reaction
product of Compound (IX) and Alcohol Derivative (X). The reaction
is usually conducted in an inert solvent such as toluene,
tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and the
like. The reaction temperature is usually -30 to +100.degree. C.,
preferably 0 to 50.degree. C. After the reaction, the product can
be isolated by conducting conventional method. Further, the product
can be purified, for example, by chromatography, recrystallization,
distillation, and the like.
[0068] As an alternative method, Ester Derivative (VII) can be
obtained by reacting carboxylic acid derivative with alcohol
derivative in the presence of deacidifying agent, and then
optionally deprotecting the reaction product.
[0069] For example, Ester Derivative (VII'') can be obtained by
reacting Compound (XI) with Compound (XII) in the presence of
deacidifying agent, and if G.sup.5 is the protecting group of
hydroxyl group,
[0070] further subjecting the reaction product obtained by the
reaction above to deprotection. The amount of Compound (XII) is
usually 1 to 2 gram equivalents, preferably 1 to 1.5 gram
equivalents, per 1 gram equivalent of Compound (XI). The amount of
deacidifying agent is usually 1 to 5 gram equivalents, preferably 1
to 3 gram equivalents, per 1 gram equivalent of Compound (XI).
[0071] The reaction of Compound (XI) with Compound (XII) is usually
conducted in an inert solvent such as toluene, tetrahydrofuran,
dimethylformamide, dimethylsulfoxide, and the like. Examples of the
deacidifying agent include organic base such as amines (e.g.
triethylamine, etc.), pyridines (e.g. pyridine, picoline, etc.),
and the like, inorganic base such as alkali metal hydroxide (e.g.
sodium hydroxide, potassium hydroxide, etc.), alkali metal
carbonate (e.g. potassium carbonate, sodium carbonate, etc.), and a
mixture thereof.
[0072] The reaction can be conducted, for example, by a method of
adding a deacidifying agent into a solution of Compound (XI) and
Compound (XII) in a solvent. Alternatively it can also be conducted
by a method of adding Compound (XI) into a solution of Compound
(XII) and deacidifying agent in a solvent.
[0073] The reaction temperature is usually -30 to +200.degree. C.,
preferably 0 to 150.degree. C. The reaction can be conducted in the
presence of phase transfer catalysts such as tetrabutylammonium
bromide.
[0074] After the reaction, the product can be isolated by
conducting conventional method such as neutralization, extraction,
crystallization, condensation, and the like. Further, the product
can be purified, for example, by recrystallization, chromatography,
and the like.
[0075] When G.sup.5 is the protecting group of hydroxyl group, the
product obtained is subjected to deprotection reaction. The
reaction can be conducted in a conventional manner. For example,
when the protecting group of hydroxyl group is trimethylsilyl
group, it can be performed by using desilylating agent such as
tetrabutylammonium fluoride. The amount of the desilylating agent
is usually 1 to 10 gram equivalents, preferably 1 to 2 gram
equivalents, per 1 gram equivalent of the reaction product of
Compound (XI) and Compound (XII). The reaction is usually conducted
in an inert solvent such as toluene, tetrahydrofuran,
dimethylformamide, dimethylsulfoxide, and the like. The reaction
temperature is usually -30 to +100.degree. C., preferably 0 to
50.degree. C. After the reaction, the product can be isolated by
conducting conventional method. Further, the product can be
purified, for example, by chromatography, recrystallization,
distillation, and the like.
[0076] Next, resin components constituting the present composition
will be explained. The resin used in the present composition
contains a structural unit having an acid-labile group and the
resin is insoluble or poorly soluble itself in alkali aqueous
solution and shows partial dissociation of groups by the action of
an acid to become soluble in alkali aqueous solution after the
dissociation. The acid-labile group can be selected from
conventionally known various groups.
[0077] Specifically, various carboxylate groups (--COOR) are
mentioned as the acid-labile group, and examples thereof include
tertiary alky carboxylate groups such as tert-butyl carboxylate
group; acetal type carboxylate groups such as methoxymethyl
carboxylate group, ethoxymethyl carboxylate group, 1-ethoxyethyl
carboxylate group, 1-isobutoxyethyl carboxylate group,
1-isopropoxyethyl carboxylate group, 1-ethoxypropyl carboxylate
group, 1-(2-methoxyethoxy)ethyl carboxylate group,
1-(2-acetoxyethoxy)ethyl carboxylate group,
1-[2-(1-adamantyloxy)ethoxy]ethyl carboxylate group,
1-[2-(1-adamantanecarbonyloxy)ethoxy]ethyl carboxylate group,
tetrahydro-2-furyl carboxylate group and tetrahydro-2-pyranyl
carboxylate group; alicyclic esters such as isobornyl carboxylate
group, 2-alkyl-2-adamantyl carboxylate group,
1-(1-adamantyl)-1-alkylalkyl carboxylate group, and the like.
[0078] Monomers to be derived into structural units having such
carboxylate group (--COOR) may be (meth)acryl-based monomers such
as methacrylates and acrylates, or those obtained by bonding of a
carboxylate group to alicyclic monomer such as
norbornenecarboxylate, tricyclodecenecarboxylate and
tetracyclodecenecarboxylate.
[0079] Among the above-mentioned monomers, it is preferable to use
those having a bulky group containing alicyclic group such as, for
example, 2-alkyl-2-adamantyl group and 1-(1-adamantyl)-1-alkylalkyl
group, as the group dissociated by the action of an acid, since
excellent resolution is obtained when used in the present
composition.
[0080] Examples of such monomer containing a bulky group include
2-alkyl-2-adamantyl(meth)acrylate,
1-(1-adamantyl)-1-alkylalkyl(meth)acrylate, 2-alkyl-2-adamantyl
5-norbornene-2-carboxylate, 1-(1-adamantyl)-1-alkylalkyl
5-norbornene-2-carboxylate, 2-alkyl-2-adamantyl
.alpha.-chloroacrylate, 1-(1-adamantyl)-1-alkylalkyl
.alpha.-chloroacrylate, and the like.
[0081] Particularly when 2-alkyl-2-adamantyl(meth)acrylate or
2-alkyl-2-adamantyl .alpha.-chloroacrylate is used as the monomer
for the resin component in the present composition, excellent
resolution is obtained. Typical examples of such
2-alkyl-2-adamantyl(meth)acrylate and 2-alkyl-2-adamantyl
.alpha.-chloroacrylate include 2-methyl-2-adamantyl acrylate,
2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate,
2-ethyl-2-adamantyl methacrylate, 2-n-butyl-2-adamantyl acrylate,
2-methyl-2-adamantyl .alpha.-chloroacrylate, 2-ethyl-2-adamantyl
.alpha.-chloroacrylate, and the like. When particularly
2-ethyl-2-adamantyl(meth)acrylate or 2-ethyl-2-adamantyl
.alpha.-chloroacrylate is used for the present composition, balance
between sensitivity and heat resistance is excellent. In the
present invention, two or more kind of monomers having group
dissociated by the action of an acid may be used together, if
necessary.
[0082] 2-alkyl-2-adamantyl(meth)acrylate can usually be produced by
reacting 2-alkyl-2-adamantanol or metal salt thereof with an
acrylic halide or methacrylic halide.
[0083] The resin used for the present composition can also contain,
in addition to the above-mentioned structural units having an
acid-labile group, other structural units not dissociated or not
easily dissociated by the action of an acid. Examples of such other
structural units which can be contained include structural units
derived from monomers having a free carboxyl group such as acrylic
acid and methacrylic acid, structural units derived from aliphatic
unsaturated dicarboxylic anhydrides such as maleic anhydride and
itaconic anhydride, structural unit derived from 2-norbornene,
structural unit derived from (meth)acrylonitrile, and the like.
[0084] As it causes no problem on light absorption in the case of
KrF exposure, a structural unit derived from hydroxystyrene can be
further contained.
[0085] Particularly, to contain, in addition to the structural unit
having an acid-labile group, further at least one structural unit
selected from the group consisting of a structural unit derived
from p-hydroxystyrene, a structural unit derived from
m-hydroxystyrene, a structural unit derived from
3-hydroxy-1-adamantyl(meth)acrylate, a structural unit derived from
3,5-dihydroxy-1-adamantyl(meth)acrylate, a structural unit derived
from (meth)acryloyloxy-.gamma.-butyrolactone having a lactone ring
optionally substituted by alkyl group, a structural unit of the
following formula (a) and a structural unit of the following
formula (b), in the resin in the present composition, is preferable
from the standpoint of the adhesiveness of resist to a substrate.
##STR29## In the formulae (a) and (b), R.sup.40 and R.sup.41 each
independently represents hydrogen atom, alkyl group having 1 to 4
carbon atoms or perfluoroalkyl group having 1 to 4 carbon atoms,
R.sup.50 and R.sup.51 each independently represents methyl group,
trifluoromethyl group or halogen atom, and p represents an integer
of 1 to 3. When p is 2 or 3, each of R.sup.50 may be the same or
different, and each of R.sup.51 may be the same or different.
[0086] 3-Hydroxy-1-adamantyl(meth)acrylate and
3,5-dihydroxy-1-adamantyl (meth)acrylate can be produced by, for
example, reacting corresponding hydroxyadamantane with
(meth)acrylic acid or its acid halide, and they are also
commercially available.
[0087] Further, (meth)acryloyloxy-.gamma.-butyrolactone can be
produced by reacting .alpha.- or .beta.-bromo-.gamma.-butyrolactone
having a lactone ring optionally substituted by alkyl with acrylic
acid or methacrylic acid, or reacting .alpha.- or
.beta.-hydroxy-.gamma.-butyrolactone having a lactone ring
optionally substituted by alkyl with acrylic halide or methacrylic
halide.
[0088] As monomers to be derived into structural units of the
formulae (a) and (b), specifically listed are, for example,
(meth)acrylates of alicyclic lactones having hydroxyl group
described below, and mixtures thereof, and the like. These esters
can be produced, for example, by reacting corresponding alicyclic
lactone having hydroxyl group with (meth)acrylic acids, and the
production method thereof is described in, for example,
JP2000-26446A. ##STR30##
[0089] When any of the structural unit derived from
3-hydroxy-1-adamantyl (meth)acrylate, the structural unit derived
from 3,5-dihydroxy-1-adamantyl (meth)acrylate, the structural unit
derived from .alpha.-(meth)acryloyloxy-.gamma.-butyrolactone, the
structural unit derived from
.beta.-(meth)acryloyloxy-.gamma.-butyrolactone and the structural
unit of the formulae (a) and (b) is contained in the resin, not
only the adhesiveness of the resist to a substrate is improved, but
also the resolution of the resist is improved.
[0090] Here, examples of the
(meth)acryloyloxy-.gamma.-butyrolactone include
.alpha.-acryloyloxy-.gamma.-butyrolactone,
.alpha.-methacryloyloxy-.gamma.-butyrolactone,
.alpha.-acryloyloxy-.beta.,.beta.-dimethyl-.gamma.-butyrolactone,
.alpha.-methacryloyloxy-.beta.,.beta.-dimethyl-.gamma.-butyrolactone,
.alpha.-acryloyloxy-.alpha.-methyl-.gamma.-butyrolactone,
.alpha.-methacryloyloxy-.alpha.-methyl-.gamma.-butyrolactone,
.beta.-acryloyloxy-.gamma.-butyrolactone,
.beta.-methacryloyloxy-.gamma.-butyrolactone,
.beta.-methacryloyloxy-.alpha.-methyl-.gamma.-butyrolactone and the
like.
[0091] In the case of KrF excimer laser exposure, sufficient
transmittance can be obtained even the structural unit derived from
hydroxystyrene is contained in the resin. Specifically,
copolymerization resins containing a structural unit derived from
p- or m-hydroxystyrene as described below are listed. For obtaining
such copolymerization resins, the corresponding (meth)acrylic ester
monomer can be radical-polymerized with acetoxystyrene and styrene,
and then the reaction mixture can be de-acetylated with an acid.
##STR31## ##STR32## ##STR33##
[0092] In these cases, it is advantageous from the standpoint of
dry etching resistance to contain 2-alkyl-2-adamantyl group or
1-(1-adamantyl)-1-alkylalkyl group as the acid labile group in the
resin.
[0093] The resin containing a structural unit derived from
2-norbornene shows strong structure because of alicyclic group
directly present on its main chain and shows a property that dry
etching resistance is excellent. The structural unit derived from
2-norbornene can be introduced into the main chain by radical
polymerization using, for example, in addition to corresponding
2-norbornene, aliphatic unsaturated dicarboxylic anhydrides such as
maleic anhydride and itaconic anhydride together. The structural
unit derived from 2-norbornene is formed by opening of its double
bond, and can be represented by the formula (c). The structural
unit derived from maleic anhydride and the structural unit derived
from itaconic anhydride which are the structural unit derived from
aliphatic unsaturated dicarboxylic anhydrides are formed by opening
of their double bonds, and can be represented by the formula (d)
and the formula (e), respectively. ##STR34##
[0094] Here, R.sup.52 and R.sup.53 in the formula (c) each
independently represent hydrogen atom, alkyl group having 1 to 3
carbon atoms, hydroxyalkyl group having 1 to 3 carbon atoms,
carboxyl group, cyano group or --COOU group in which U represents
alcohol residue, or R.sup.52 and R.sup.53 can bond together to form
a carboxylic anhydride residue represented by
--C(.dbd.O)OC(.dbd.O)--.
[0095] In R.sup.52 and R.sup.53, examples of the alkyl group
include methyl group, ethyl group, propyl group and isopropyl
group, specific examples of hydroxyalkyl group include
hydroxymethyl group, 2-hydroxyethyl group and the like.
[0096] In R.sup.52 and R.sup.53, --COOU group is an ester formed
from carboxyl group, and as the alcohol residue corresponding to U,
for example, optionally substituted alkyl groups having about 1 to
8 carbon atoms, 2-oxooxolan-3- or -4-yl group and the like are
listed, and as the substituent on the alkyl group, hydroxyl group,
alicyclic hydrocarbon residues and the like are listed.
[0097] Specific examples of --COOU include methoxycarbonyl group,
ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group,
tert-butoxycarbony group, 2-oxooxalan-3-yloxycarbonyl group,
2-oxooxalan-4-yloxycarbonyl group, 1,1,2-trimethylpropoxycarbonyl
group, 1-cyclohexyl-1-methylethoxycarbonyl group,
1-(4-methylcyclohexyl)-1-methylethoxycarbonyl group,
1-(1-adamantyl)-1-methylethoxycarbonyl group and the like.
[0098] Specific examples of the monomer used to derive the
structural unit represented by the formula (VIII) may include the
followings; [0099] 2-norbornene, [0100] 2-hydroxy-5-norbornene,
[0101] 5-norbornen-2-carboxylic acid, [0102] methyl
5-norbornen-2-carboxylate, [0103] t-butyl
5-norbornen-2-carboxylate, [0104] 1-cyclohexyl-1-methylethyl
5-norbornen-2-carboxylate, [0105]
1-(4-methylcyclohexyl)-1-methylethyl 5-norbornen-2-carboxylate,
[0106] 1-(4-hydroxycyclohexyl)-1-methylethyl
5-norbornen-2-carboxylate, [0107] 1-methyl-1-(4-oxocyclohexyl)ethyl
5-norbornen-2-carboxylate, [0108] 1-(1-adamantyl)-1-methylethyl
5-norbornen-2-carboxylate, [0109] 1-methylcyclohexyl
5-norbornen-2-carboxylate, [0110] 2-methyl-2-adamantyl
5-norbornen-2-carboxylate, [0111] 2-ethyl-2-adamantyl
5-norbornen-2-carboxylate, [0112] 2-hydroxyethyl
5-norbornen-2-carboxylate, [0113] 5-norbornen-2-methanol, [0114]
5-norbornen-2,3-dicarboxylic acid anhydride, and the like.
[0115] The resin used in the present composition preferably
contains structural unit(s) having an acid-labile group generally
in a ratio of 10 to 80% by mol in all structural units of the resin
though the ratio varies depending on the kind of radiation for
patterning exposure, the kind of an acid-labile group, and the
like.
[0116] When the structural units particularly derived from
2-alkyl-2-adamantyl (meth)acrylate or
1-(1-adamantyl)-1-alkylalkyl(meth)acrylate are used as the
acid-labile group, it is advantageous that the ratio of the
structural units is 15% by mol or more in all structural units of
the resin.
[0117] When, in addition to structural units having an acid-labile
group, other structural units not easily dissociated by the action
of an acid, for example, a structural unit derived from
3-hydroxy-1-adamantyl(meth)acrylate, a structural units derived
from 3,5-dihydroxy-1-adamantyl(meth)acrylate or
.alpha.-(meth)acryloyloxy-.gamma.-butyrolactone, a structural units
derived from .beta.-(meth)acryloyloxy-.gamma.-butyrolactone, a
structural unit of the formula (a) or (b), a structural unit
derived from hydroxystyrene, a structural unit of the formula (c),
a structural unit derived from maleic anhydride of the formula (d)
which is a structural unit derived from an aliphatic unsaturated
dicarboxylic anhydride, a structural unit derived from itaconic
anhydride of the formula (e) and the like are contained, it is
preferable that the sum of these structural units is in the range
of 20 to 90% by mol based on all structural units of the resin.
[0118] When 2-norbornenes and aliphatic unsaturated dicarboxylic
anhydride are used as copolymerization monomer, it is preferable to
use them in excess amount in view of a tendency that these are not
easily polymerized.
[0119] As balance between sensitivity and resolution becomes
excellent, it is preferred to use polymer obtained by
copolymerizing two kind of monomers having different acid-labile
groups as the polymer component of the present composition.
[0120] The acid generator, another component of the present
composition, is the compound which is decomposed to generate an
acid by allowing radioactive ray such as light and electron beam to
act on the acid generator itself or a resist composition containing
the acid generator. The acid generated from the acid generator acts
on the polymer component above, to dissociate acid-labile group
present in polymer component.
[0121] Such acid generators include, for example, onium salt,
organic halogen compounds, sulfone compounds, sulfonate compounds,
and the like.
[0122] Specific examples thereof include the followings:
[0123] diphenyliodonium trifluoromethanesulfonate,
4-methoxyphenylphenyliodinium hexafluoroantimonate,
4-methoxyphenylphenyliodinium trifluoromethanesulfonate,
bis(4-tert-butylphenyl)iodonium tetrafluoroborate
bis(4-tert-butylphenyl)iodonium hexafluorophosphate,
bis(4-tert-butylphenyl)iodonium hexafluoroantimonate
bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate,
triphenylsulfonium hexafluorophosphate, triphenylsulfonium
hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate,
triphenylsulfonium
adamantanemethoxycarbonyldifluoromethylsulfonate,
triphenylsulfonium
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethanesulfonate,
triphenylsulfonium
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difl-
uoromethanesulfonate, triphenylsulfonium
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate,
4-methoxyphenyldiphenylsulfonium hexafluoroantimonate,
4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate,
p-tolyldiphenylsulfonium trifluoromethanesulfonate,
p-tolyldiphenylsulfonium perfluorobutanesulfonate,
p-tolyldiphenylsulfonium perfluorooctanesulfonate,
2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate,
4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate,
4-phenylthiophenyldiphenylsulfonium hexafluorophosphate,
4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate,
1-(2-naphtholylmethyl)thiolanium hexafluoroantimonate,
1-(2-naphtholylmethyl)thiolanium trifluoromethanesulfonate,
4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate,
4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium
trifluoromethanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium
perfluorobutanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium
perfluorootcanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium
trifluoromethanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium
perfluorobutanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium
perfluorooctanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate,
2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine,
2,4,6-tris(trichloromethyl)-1,3,5-triazine
2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(benzo[d][1,3]dioxolan-5-yl)-4,6-bis(trichloromeythyl)-1,3,5-triazine,
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-pentyloxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
1-benzoyl-1-phenylmethyl p-toluenesulfonate (generally called
"benzoin tosylate"), 2-benzoyl-2-hydroxy-2-phenylethyl
p-toluenesulfonate (generally called .alpha.-methylolbenzoin
tosylate), 1,2,3-benzene-tri-yl tris(methanesulfonate),
2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl
p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate, diphenyl
disulfone, di-p-tolyl disulfone bis(phenylsulfonyl)diazomethane,
bis(4-chlorophenylsulfonyl)diazomethane,
bis(p-tolylsulfonyl)diazomethane,
bis(4-tert-butylphenylsulfonyl)diazomethane,
bis(2,4-xylylsulfonyl)diazomethane,
bis(cyclohexylsulfonyl)diazomethane,
(benzoyl)(phenylsulfonyl)diazomethane,
N-(phenylsulfonyloxy)succinimide,
N-(trifluoromethylsulfonyloxy)succinimide,
N-(trifluoromethylsulfonyloxy)phthalimide,
N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxyimide,
N-(trifluoromethylsulfonyloxy)naphthalimide,
N-(10-camphorsulfonyloxy)naphthalimide, and the like.
[0124] In the present composition, performance deterioration caused
by inactivation of acid which occurs due to post exposure delay can
be diminished by adding basic compounds, particularly, basic
nitrogen-containing organic compounds, for example, amines as a
quencher.
[0125] Specific examples of such basic nitrogen-containing organic
compounds include the ones represented by the following formulae:
##STR35##
[0126] In the formulas, T.sup.12 and T.sup.13 each independently
represents a hydrogen atom, an alkyl group, a cycloalkyl group or
an aryl group. The alkyl group preferably has about 1 to 6 carbon
atoms, the cycloalkyl group preferably has about 5 to 10 carbon
atoms, and the aryl group preferably has about 6 to 10 carbon
atoms. Furthermore, at least one hydrogen atom on the alkyl group,
cycloalkyl group or aryl group may each independently be
substituted with hydroxyl group, amino group, or alkoxy group
having 1 to 6 carbon atoms. At least one hydrogen atom on the amino
group may each independently be substituted with alkyl group having
1 to 4 carbon atoms.
[0127] T.sup.14, T.sup.15 and T.sup.16 each independently
represents a hydrogen atom, an alkyl group, a cycloalkyl group, an
aryl group or an alkoxy group. The alkyl group preferably has about
1 to 6 carbon atoms, the cycloalkyl group preferably has about 5 to
10 carbon atoms, the aryl group preferably has about 6 to 10 carbon
atoms, and the alkoxy group preferably has about 1 to 6 carbon
atoms. Furthermore, at least one hydrogen atom on the alkyl group,
cycloalkyl group, aryl group or alkoxy group may each independently
be substituted with hydroxyl group, amino group, or alkoxy group
having 1 to 6 carbon atoms. At least one hydrogen atom on the amino
group may be substituted with alkyl group having 1 to 4 carbon
atoms.
[0128] T.sup.17 represents an alkyl group or a cycloalkyl group.
The alkyl group preferably has about 1 to 6 carbon atoms, and the
cycloalkyl group preferably has about 5 to 10 carbon atoms.
Furthermore, at least one hydrogen atom on the alkyl group or
cycloalkyl group may each independently be substituted with
hydroxyl group, amino group, or alkoxy group having 1 to 6 carbon
atoms. At least one hydrogen atom on the amino group may be
substituted with alkyl group having 1 to 4 carbon atoms.
[0129] In the formulas, T.sup.18 represents an alkyl group, a
cycloalkyl group or an aryl group. The alkyl group preferably has
about 1 to 6 carbon atoms, the cycloalkyl group preferably has
about 5 to 10 carbon atoms, and the aryl group preferably has about
6 to 10 carbon atoms. Furthermore, at least one hydrogen atom on
the alkyl group, cycloalkyl group or aryl group may each
independently be substituted with a hydroxyl group, an amino group,
or an alkoxy group having 1 to 6 carbon atoms. At least one
hydrogen atom on the amino group may each independently be
substituted with alkyl group having 1 to 4 carbon atoms.
[0130] However, none of T.sup.12 and T.sup.13 in the compound
represented by the above formula [3] is a hydrogen atom.
[0131] A represents alkylene group, carbonyl group, imino group,
sulfide group or disulfide group. The alkylene group preferably has
about 2 to 6 carbon atoms.
[0132] Moreover, among T.sup.12-T.sup.18, in regard to those which
can be straight-chained or branched, either of these may be
permitted.
[0133] T.sup.19, T.sup.20 and T.sup.21 each independently
represents a hydrogen atom, an alkyl group having 1 to 6 carbon
atoms, an aminoalkyl group having 1 to 6 carbon atoms, a
hydroxyalkyl group having 1 to 6 carbon atoms or a substituted or
unsubstituted aryl group having 6 to 20 carbon atoms, or T.sup.19
and T.sup.20 bond to form an alkylene group which forms a lactam
ring together with adjacent --CO--N--.
[0134] Examples of such compounds include hexylamine, heptylamine,
octylamine, nonylamine, decylamine, aniline, 2-, 3- or
4-methylaniline, ethylenediamine, tetramethylenediamine,
hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane,
4,4'-diamino-3,3'-dimethyldiphenylmethane,
4,4'-diamino-3,3'-diethyldiphenylmethane, dibutylamine,
dipentylamine, dihexylamine, diheptylamine, dioctylamine,
dinonylamine, didecylamine, N-methylaniline, piperidine,
diphenylamine, triethylamine, trimethylamine, tripropylamine,
tributylamine, tripentylamine, trihexylamine, triheptylamine,
trioctylamine, trinonylamine, tridecylamine, methyldibutylamine,
methyldipentylamine, methyldihexylamine, methyldicyclohexylamine,
methyldiheptylamine, methyldioctylamine, methyldinonylamine,
methyldidecylamine, ethyldibutylamine, ethydipentylamine,
ethyldihexylamine, ethydiheptylamine, ethyldioctylamine,
ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine,
tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine,
N,N-dimethylaniline, 2,6-isopropylaniline, pyridine,
4-methylpyridine, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl
ketone, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane,
1,3-di(4-pyridyl)propane, 1,2-bis(2-pyridyl)ethylene,
1,2-bis(4-pyridyl)ethylene, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl
disulfide, 1,2-bis(4-pyridyl)ethylene, 2,2'-dipicolylamine,
3,3'-dipicolylamine, tetramethylammonium hydroxide,
tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide,
tetra-n-hexylammonium hydroxide, tetra-n-octylammonium hydroxide,
phenyltrimethylammonium hydroxide,
3-trifluoromethylphenyltrimethylammonium hydroxide,
(2-hydroxyethyl)trimethylammonium hydroxide (so-called "choline"),
N-methylpyrrolidone, and the like.
[0135] Furthermore, hindered amine compounds having piperidine
skeleton as disclosed in JP-A-H11-52575 can be used as
quencher.
[0136] It is preferable that the present composition contains
polymer component in an amount of about 80 to 99.8% by weight,
Supracompound (I) in an amount of 0.1 to 40% by weight and the acid
generator in an amount of 0.1 to 20% by weight based on the total
amount of polymer component, Supracompound (I) and the acid
generator.
[0137] When basic compound is used as a quencher, the basic
compound is contained preferably in an amount of about 0.001 to 1
part by weight, more preferably in an amount of about 0.01 to 0.3
part by weight based on 100 parts by weight of polymer
component.
[0138] The present composition can contain, if necessary, various
additives in small amount such as a sensitizer, solution
suppressing agent, other polymers, surfactant, stabilizer, dye and
the like, as long as the effect of the present invention is not
prevented.
[0139] The present composition is usually in the form of a resist
liquid composition in which the aforementioned ingredients are
dissolved in a solvent, and the resist liquid composition is to be
applied onto a substrate such as a silicon wafer by a conventional
process such as spin coating. The solvent used here is sufficient
to dissolve the aforementioned ingredients, have an adequate drying
rate, and give a uniform and smooth coat after evaporation of the
solvent and, hence, solvents generally used in the art can be used.
In the present invention, the total solid content means total
content exclusive of solvents.
[0140] Examples thereof include glycol ether esters such as ethyl
Cellosolve acetate, methyl Cellosolve acetate and propylene glycol
monomethyl ether acetate; ethers such as di(ethylene
glycol)dimethyl ether; esters such as ethyl lactate, butyl lactate,
amyl lactate and ethyl pyruvate and the like; ketones such as
acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone;
cyclic esters such as .gamma.-butyrolactone, and the like. These
solvents can be used each alone or in combination of two or
more.
[0141] A resist film applied onto the substrate and then dried is
subjected to exposure for patterning, then heat-treated for
facilitating a deblocking reaction, and thereafter developed with
an alkali developer. The alkali developer used here may be any one
of various alkaline aqueous solutions used in the art, and
generally, an aqueous solution of tetramethylammonium hydroxide or
(2-hydroxyethyl)trimethylammonium hydroxide (commonly known as
"choline") is often used.
[0142] It should be construed that embodiments disclosed here are
examples in all aspects and not restrictive. It is intended that
the scope of the present invention is determined not by the above
descriptions but by appended Claims, and includes all variations of
the equivalent meanings and ranges to the Claims.
[0143] The present invention will be described more specifically by
way of examples, which are not construed to limit the scope of the
present invention. The "%" and "part(s)" used to represent the
content of any component and the amount of any material used in the
following examples are on a weight basis unless otherwise
specifically noted. The weight-average molecular weight of any
material used in the following examples is a value found by gel
permeation chromatography using styrene as a standard reference
material.
EXAMPLE 1
Synthesis of PECHOM
[0144] ##STR36##
[0145] To a solution consisting of 110 g of tetracarboxylic acid
(abbreviated to "PECHA") above, which is described in JP2000-302839
A, 59 g of chloromethyl methyl ether and 500 ml of
N,N-dimethylformamide (abbreviated to "DMF"), a solution consisting
of 118 g of triethylamine (abbreviated to "TEA"), 4.4 g of
dimethylaminopyridine (abbreviated to "DMAP") and 300 ml of DMF was
added dropwise at 5 to 10.degree. C. for 2.5 hours. After stirred
overnight, the reaction mixture was diluted by water, and extracted
with ethyl acetate. The organic layer obtained was washed with
water, with sodium bicarbonate solution, and then with water. After
dried with anhydrous magnesium sulfate, the organic solution was
concentrated. The crude product obtained (132 g) was purified by
silica gel column chromatography (developer: heptane/ethyl acetate)
to obtain 102 g of tetracarboxylate (abbreviated to "PECHOM").
[0146] .sup.1H NMR(CDCl.sub.3):d1.3-1.65 (16H, cyclohexyl),
1.65-2.15 (16H, cyclohexyl), 2.75-3.0 (8H, cyclohexyl), 3.45 (12H,
s, CH.sub.3), 4.0-4.2 (8H, CH.sub.2), 5.1-5.35 (8H, CH.sub.2)
.sup.13C NMR(CDCl.sub.3):d23.32 (cyclohexyl), 23.96 (cyclohexyl),
25.73 (cyclohexyl), 26.49 (cyclohexyl), 42.04 (quaternary carbon),
42.43 (cyclohexyl), 42.56 (cyclohexyl), 57.52 (CH.sub.3), 62.42
(CH.sub.2), 90.44 (CH.sub.2), 172.97 (C.dbd.O), 173.01 (C.dbd.O)
FD-MS:930 (M+H).sup.+(C.sub.45H.sub.68O.sub.20=929.01)
EXAMPLE 2
Synthesis of PECH-AMAD
[0147] ##STR37##
[0148] A solution was prepared by adding 11.0 g of potassium
carbonate to a mixture obtained by dissolving 10.0 g of PECHA in
100 g of DMF. To the solution, a solution consisting of 14.5 g of
2-methyl-2-adamantyl chloroacetate (abbreviated to "CAMAD") and 20
g of DMF was added at room temperature. To the mixture, 3.3 g of
potassium iodide was added, and the added mixture was stirred
overnight at room temperature overnight. After the stirring, the
reaction mixture was diluted with water, then extracted with ethyl
acetate. The organic layer obtained was washed with water, dried
and decolorized with anhydrous magnesium sulfate and activated
carbon, then concentrated. The crude product obtained (21.3 g) was
purified by silica gel column chromatography (developer:
heptane/ethyl acetate) to obtain 15.5 g of tetracarboxylate
(abbreviated to "PECH-AMAD").
[0149] .sup.1H NMR (CDCl.sub.3):d1.3-1.65 (16H, cyclohexyl),
1.55-1.57 (16H, adamantyl), 1.62 (12H, s, CH.sub.3), 1.70-1.72 (8H,
adamantyl), 1.80 (8H, adamantyl), 1.70-1.89 (16H, adamantyl),
1.75-2.11 (16H, cyclohexyl), 1.95-2.03 (16H, adamantyl), 2.27-2.30
(8H, adamantyl), 2.78 (4H, m, cyclohexyl), 2.98 (4H, m,
cyclohexyl), 4.06 (8H, s, methylene), 4.41-4.71 (8H, m, methylene)
.sup.13C NMR(CDCl.sub.3):d22.14 (CH.sub.3), 23.10 (cyclohexyl),
23.89 (cyclohexyl), 25.58 (cyclohexyl), 26.42 (cyclohexyl and
adamantyl), 27.11 (adamantyl), 32.76 and 32.78 (adamantyl), 36.00
and 36.11 (adamantyl), 37.91 (adamantyl), 41.90 (quaternary
carbon), 41.94 (cyclohexyl), 42.47 (cyclohexyl), 60.80(CH.sub.2),
62.26 (CH.sub.2), 166.38 (C.dbd.O), 172.60 (C.dbd.O), 172.77
(C.dbd.O) GPC-MS:1617(M+K).sup.+
(C.sub.89H.sub.124O.sub.24=1577.92)
EXAMPLE 3
Synthesis of PECH-AHAD
[0150] ##STR38##
[0151] A solution was prepared by adding 5.5 g of potassium
carbonate to a mixture obtained by dissolving 5.0 g of PECHA in 30
g of DMF. To the solution, a solution consisting of 6.5 g of
3-hydroxyadamantyl chloroacetate (abbreviated to "CAHAD") and 32.5
g of DMF was added at room temperature. To the mixture, 1.65 g of
potassium iodide was added, and the added mixture was stirred at
40.degree. C. for 2 hours. After cooling, the reaction mixture was
diluted with water, then extracted with ethyl acetate. The organic
layer obtained was washed with water, dried with anhydrous
magnesium sulfate, and then concentrated. The crude product
obtained (12.0 g) was purified by silica gel column chromatography
(developer: ethyl acetate) to obtain 7.7 g of tetracarboxylate
(abbreviated to "PECH-AHAD").
[0152] .sup.1H NMR (CDCl.sub.3):d1.35-1.60 (16H, cyclohexyl),
1.48-1.56 (8H, adamantyl), 1.65-1.71 (16H, adamantyl), 1.71-2.13
(16H, cyclohexyl), 2.02 (16H, adamantyl), 2.11 (8H, adamantyl),
2.31 (8H, adamantyl), 2.48 (4H, OH), 2.75 (4H, m, cyclohexyl), 3.01
(4H, m, cyclohexyl), 4.07 (8H, s, methylene), 4.38-4.62 (8H, m,
methylene) .sup.13C NMR (CDCl.sub.3):d23.01 (adamantyl), 23.98
(cyclohexyl), 25.45 (cyclohexyl), 26.57 (cyclohexyl), 31.04
(adamantyl), 34.50 (cyclohexyl), 39.78 39.80 (adamantyl),
41.9242.54 (cyclohexyl), 43.65 (adamantyl), 48.74 (adamantyl),
60.98 (CH.sub.2), 62.58 (CH.sub.2), 69.93 and 69.95 (adamantyl),
82.84 (adamantyl), 166.46 (C.dbd.O), 172.65 (C.dbd.O), 173.00
(C.dbd.O)
[0153] GPC-MS:1625(M+K).sup.+
(C.sub.85H.sub.116O.sub.28=1585.81)
EXAMPLE 4
Synthesis of PECH-ANL
[0154] ##STR39##
[0155] A solution was prepared by adding 11.0 g of potassium
carbonate to a mixture obtained by dissolving 10.0 g of PECHA in 60
g of DMF. To the solution, a solution consisting of 12.3 g of
hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yl
chloroacetate (abbreviated to "CANL") and 40 g of DMF was added at
room temperature. To the mixture, 3.3 g of potassium iodide was
added, and the added mixture was stirred at room temperature
overnight. After the stirring, ethyl acetate and water was added to
the reaction mixture, then the product was extracted from the
mixture with ethyl acetate. The organic layer was washed with
ion-exchanged water, dried with anhydrous magnesium sulfate, then
concentrated under reduced pressure to obtain 19.0 g of
tetracarboxylate (abbreviated to "PECH-ANL").
[0156] .sup.1H NMR (CDCl.sub.3):d1.35-1.60 (16H, cyclohexyl), 1.64
and 1.66 (4H, norbornanelactone), 1.72 and 1.75 (4H,
norbornanelactone), 1.75-2.12 (16H, cyclohexyl), 1.99 and 2.01 (4H,
norbornanelactone), 2.03-2.06 (4H, norbornanelactone), 2.54-2.76
(4H, norbornanelactone), 2.57 (4H, m, norbornanelactone), 2.77 (4H,
m, cyclohexyl), 3.03 (4H, m, cyclohexyl), 3.22 (4H, m,
norbornanelactone), 4.06 (8H, m, methylene), 4.56 (4H, m,
norbornanelactone), 4.63 (4H, s, norbornanelactone), 4.51-4.74 (8H,
m, methylene)
[0157] .sup.13C NMR (CDCl.sub.3):d22.78 and 22.86 (cyclohexyl),
23.78 and 23.86 (cyclohexyl), 25.24&25.36 (cyclohexyl), 26.40
and 26.50 (cyclohexyl)31.24 (norbornanelactone), 33.86
(norbornanelactone), 37.72 (norbornanelactone), 40.94 and 40.96
(norbornanelactone), 41.65 and 31.68 (cyclohexyl), 41.76
(quaternary carbon), 42.33 and 42.38 (cyclohexyl), 44.72
(norbornanelactone), 60.33 (CH.sub.2), 62.30 (CH.sub.2), 79.40
(norbornanelactone), 80.09 (norbornanelactone), 166.44 (C.dbd.O),
172.60 (C.dbd.O), 172.70 (C.dbd.O), 172.29 (C.dbd.O)
[0158] GPC-MS:1569.5(M+K).sup.+
(C.sub.77H.sub.92O.sub.32=1529.54)
EXAMPLE 5
Syntheses of PECH-3-AMAD-ANL and PECH-2-AMAD-2-ANL
[0159] ##STR40##
[0160] A solution was prepared by adding 8.26 g of potassium
carbonate to a mixture obtained by dissolving 10.0 g of PECHA in 60
g of DMF. To the solution, a solution consisting of 10.78 g of
CAMAD and 40 g of DMF was added at room temperature. To the
mixture, 2.48 g of potassium iodide was added, and the added
mixture was stirred at room temperature for 2 hours. To the
mixture, CANL was added, and the added mixture was stirred at room
temperature overnight. After the stirring, ethyl acetate and water
was added to the reaction mixture, then the product was extracted
from the mixture with ethyl acetate. The organic layer was washed
with ion-exchanged water, dried with anhydrous magnesium sulfate,
then concentrated under reduced pressure. The product obtained was
purified by silica gel column chromatography to obtain 3.81 g of
tetracarboxylate3/1 (abbreviated to "PECH-3-AMAD-ANL") and 4.14 g
of tetracarboxylate2/2 (abbreviated to "PECH-2-AMAD-2-ANL").
[0161] GPC-MS: (PECH-3-AMAD-ANL) 1603.5(M+K).sup.+
(C.sub.86H.sub.124O.sub.26=1565.83)
[0162] GPC-MS: (PECH-2-AMAD-2-ANL) 1591.5(M+K).sup.+
(C.sub.83H.sub.108O.sub.28=1553.73)
EXAMPLE 6
Synthesis of GLUCH-5AMAD
[0163] ##STR41##
[0164] To a mixture of 20.0 g of D-glucose, 3.4 g of
4-(N,N-dimethylamino)pyridine, 68.0 g of TEA and 440 g of THF, a
solution of 86.0 g of cis-1,2-cyclohexanedicarboxylic anhydride and
88 g of THF was added with stirring at room temperature, then the
added mixture was stirred for 3 days. After the stirring, the
solvent was removed from the resulting mixture under reduced
pressure. To the concentrate, 600 g of chloroform and 300 g of
ion-exchanged water was added, and was neutralized with
hydrochloric acid. The neutralized organic layer was separated,
washed with ion-exchanged water, and dried with anhydrous magnesium
sulfate. Then the solvent was removed from the dried organic layer
to obtain 160.1 g of crude pentakis-D-glucose
(2-carboxycyclohexyl)carboxylate (abbreviated to "GLUCHA").
[0165] A solution was prepared by adding 10.36 g of potassium
carbonate to a mixture obtained by dissolving 9.50 g of GLUCHA in
70 g of DMF. To the solution, a solution consisting of 13.62 g of
CAMAD and 40 g of DMF was added at room temperature. To the
mixture, 3.11 g of potassium iodide was added, and the added
mixture was stirred at room temperature overnight. After the
stirring, ethyl acetate and ion-exchanged water was added to the
reaction mixture, then the product was extracted from the mixture
with ethyl acetate. The organic layer was washed with ion-exchanged
water, dried with anhydrous magnesium sulfate, then concentrated
under reduced pressure. The product obtained was purified by silica
gel column chromatography to obtain 2.68 g of pentacarboxylate
(abbreviated to "GLUCH-5AMAD").
[0166] GPC-MS: (GLUCH-5 AMAD) 2019.7(M+K).sup.+
(C.sub.111H.sub.152O.sub.31=1982.38)
EXAMPLE 7
Synthesis of GLUCH-4-AMAD
[0167] ##STR42##
[0168] The experiment was conducted in the same manner as in
Example 6 except that the amount of cis-1,2-cyclohexanedicarboxylic
anhydride and of CAMAD were changed to obtain GLUCH-4 AMAD.
[0169] GPC-MS: (GLUCH-4 AMAD) 1659.7(M+K).sup.+
(C.sub.90H.sub.124O.sub.26=1621.93)
EXAMPLE 8
Synthesis of PENB04 AMAD
[0170] ##STR43##
[0171] After suspending 20.0 g of pentaerythritol in 444 g of THF,
3.6 g of DMAP and 74.3 g of TEA were added to the suspension. To
the added suspension, a solution of 97.4 g of
5-norbornen-2,3-dicarboxylic anhydride (abbreviated to "NBEAD") and
88.8 g of THF was added dropwise. After the mixture was stirred
overnight, the stirring was maintained at 40.degree. C. for 3
hours. The reaction mixture was diluted with dilute hydrochloric
acid. The diluted mixture was extracted with chloroform, then the
organic layer obtained was dried with anhydrous magnesium sulfate.
Chloroform was evaporated from the organic layer to obtain 122.4 g
of tetracarboxylic acid (abbreviated to "PENBEA").
[0172] 110 g of PENBEA obtained above was dissolved in 552 g of
methanol, and was catalytically hydrogenated using 3.16 g of
platinum dioxide. After absorbing preliminarily determined amount
of hydrogen, the catalyst was filtrated off. The filtrate was
concentrated to obtain 109.7 g of tetracarboxylic acid (abbreviated
to "BENBA").
[0173] LC-MS: (PENBA) 839.2(M+K).sup.+
(C.sub.41H.sub.52O.sub.16=800.84)
[0174] 16.0 g of PENBA obtained above was dissolved in 143.2 g of
DMF. 21.34 g of CAMAD, 16.57 g of potassium carbonate and 0.33 g of
potassium carbonate were added thereto, and the mixture was stirred
at 40.degree. C. for 4 hours. The mixture was further stirred at
room temperature overnight. The resulting mixture was diluted with
water, and then was extracted with ethyl acetate. The organic layer
was washed with water, dried with anhydrous magnesium sulfate, and
then concentrated. The concentrate was purified by silica gel
column chromatography to obtain 9.1 g of tetraester compound
(abbreviated to "PENB-4 AMAD"). (Melting Point: 97-98.degree.
C.)
[0175] .sup.1H NMR(CDCl.sub.3):d1.45-2.10(72H, adamantyl and
norbornyl), 1.63(12H, CH.sub.3), 2.29(8H, m, adamantyl),
2.55-2.61(8H, norbornyl), 2.97-3.13(8H, norbornyl), 3.61(8H, s,
methylene), 4.39-4.67(8H, m, methylene)
[0176] .sup.13C NMR (CDCl.sub.3):d22.13 (CH.sub.3), 23.78 and 23.82
(norbornyl), 26.42 (adamantyl), 27.1 (adamantyl), 32.79
(adamantyl), 34.34 (adamantyl), 36.09 (adamantyl), 37.93
(adamantyl), 39.73 (norbornyl), 40.07&40.14 (norbornyl), 40.23
(norbornyl), 46.30 and 6.42 (norbornyl), 51.07 (CH.sub.2), 60.73
(CH.sub.2), 88.70 (adamantyl), 166.41 (C.dbd.O), 171.68 (C.dbd.O),
172.63 (C.dbd.O)
[0177] LC-MS: (PENB-4 AMAD)1663.6(M+K).sup.+
(C.sub.93H.sub.124O.sub.24=1625.97)
EXAMPLE 9
Synthesis of PENB-3 AMAD
[0178] ##STR44##
[0179] The experiment was conducted in the same manner as in
Example 8 except that the amount of NBEAD and of CAMAD were changed
to obtain triester compound (abbreviated to "PENB-3 AMAD") via
tricarboxylic acid (abbreviated to "PENB-3 A"). (melting point:
96-98.degree. C.)
[0180] LC-MS: (PENB-3A) 673.1(M+K).sup.+
(C.sub.32H.sub.42O.sub.13=634.67)
[0181] LC-MS: (PENB-3AMAD)1291.5 (M+K).sup.+
(C.sub.71H.sub.96O.sub.19=1253.51)
[0182] .sup.1H NMR (CDCl.sub.3):d1.45-2.10 (54H, adamantyl and
norbornyl), 1.62 (9H, CH.sub.3), 2.28 (6H, m, adamantyl), 2.54-2.63
(6H, norbornyl), 2.78 (1H, OH), 2.96-3.13 (6H, norbornyl), 3.47
(2H, m, methylene), 3.93-4.12 (6H, m, methylene), 4.34-4.73 (6H, m,
methylene)
[0183] .sup.13C NMR (CDCl.sub.3):d22.25 (CH.sub.3), 23.69 and 24.06
(norbornyl), 26.49 (adamantyl), 27.19 (adamantyl), 32.87
(adamantyl), 34.42 (adamantyl), 36.12 and 36.22 (adamantyl), 37.99
(adamantyl), 39.76 (norbornyl), 40.11 (norbornyl), 40.23
(norbornyl), 40.36 and 40.39 and 40.44 and 40.48 (norbornyl), 43.30
(quaternary carbon), 46.31 and 46.72 (norbornyl), 60.27 (CH.sub.2),
60.83 (CH.sub.2), 62.11 (CH.sub.2), 88.97 (adamantyl), 166.56 and
166.59 and 166.61 (C.dbd.O), 171.82 and 171.83 and 171.87
(C.dbd.O), 172.18 and 172.23 (C.dbd.O)
EXAMPLE 10
Synthesis of PENB-2AMAD-2AHAD
[0184] ##STR45##
[0185] 40.0 g of PENBA was dissolved in 392 g of DMF. 25.5 of
CAMAD, 41.4 g of potassium carbonate and 0.83 g of potassium
carbonate were added thereto, and the mixture was stirred at
40.degree. C. for 5.5 hours. The mixture was further stirred at
room temperature overnight. To the reaction mixture, 25.7 g of
CAHAD was added, and the added mixture was stirred at 40.degree. C.
for 5.5 hours. The mixture was further stirred at room temperature
overnight. The resulting mixture was diluted with water, and then
was extracted with ethyl acetate. The organic layer was washed with
water, dried with anhydrous magnesium sulfate, and then
concentrated. The concentrate was purified by silica gel column
chromatography to obtain 5.5 g of tetraester2/2 compound
(abbreviated to "PENB-2AMAD-2AHAD").
[0186] GPC-MS: (PENB-2-AMAD-2AHAD) 1670.9(M+K).sup.+
(C.sub.90H.sub.118O.sub.27=1631.88)
EXAMPLE 11
Synthesis of PENB-2AMAD-AHAD
[0187] ##STR46##
[0188] The experiment was conducted in the same manner as in
Example 10 except that the amount of CAMAD and of CAHAD were
changed to obtain triester2/1 compound (abbreviated to
"PENB-2AMAD-AHAD").
[0189] GPC-MS: (PENB-2-AMAD-AHAD) 1294(M+K).sup.+
(C.sub.70H.sub.94O.sub.20=1255.48)
EXAMPLE 12
Synthesis of PECH-CHX
[0190] ##STR47##
[0191] 2.0 g of PECHA and 1.9 g of thionyl chloride were mixed in
50 ml of toluene. The mixture was refluxed for 0.5 hour. The
resulting mixture was concentrated under reduced pressure to obtain
carboxylic acid halide (abbreviated to "PECHC"). .sup.1H NMR
(CDCl.sub.3):d1.47-1.50 (16H, cyclohexyl), 1.82-2.11 (16H,
cyclohexyl), 3.01 (4H, cyclohexyl), 3.19 (4H, cyclohexyl),
4.07-4.18 (8H, methylene)
[0192] .sup.13C NMR (CDCl.sub.3):d23.11&23.42 (cyclohexyl),
25.98 (cyclohexyl), 26.61 (cyclohexyl), 42.19 (quaternary carbon),
43.42 (cyclohexyl), 53.98 (cyclohexyl), 61.92 (methylene), 171.83
(C.dbd.O from ester), 175.02 (C.dbd.O from acid halide)
[0193] GPC-MS: (PECHC) 863(M+K).sup.+
(C.sub.37H.sub.48Cl.sub.4O.sub.12=826.58)
[0194] To a solution consisting of 1.6 g of cyclohexanol, 1.6 g of
triethylamine and 20 ml of THF, a solution consisting of 2.9 g of
PECHC and 20 ml of THF was added dropwise. After stirred for three
days, the reaction mixture was diluted with water, and then
extracted with ethyl acetate. The organic layer obtained was washed
with water, dried with anhydrous magnesium sulfate, and then
concentrated. 3.2 g of the crude product obtained was purified by
silica gel column chromatography (developer: hexane/ethyl acetate)
to obtain 1.5 g of tetraester (abbreviated to "PECH--CHX"). GPC-MS:
(PECH--CHX) 1120(M+K).sup.+ (C.sub.61H.sub.92O.sub.16=1081.37)
EXAMPLE 13
Synthesis of PENBOM
[0195] ##STR48##
[0196] To a solution obtained by dissolving 30 g of PENBA and 15.1
g of chloromethyl methyl ether in 150 ml of DMF, a solution
consisting of 30.3 g of TEA, 1.2 g of DMAP and 50 ml of DMF was
added dropwise at 3 to 8.degree. C. for 3 hours. After stirred at
room temperature overnight, the reaction mixture was diluted with
water, and then extracted with ethyl acetate. The organic layer
obtained was washed with water, with sodium bicarbonate solution,
and with Water. The washed layer was dried with anhydrous magnesium
sulfate, and then concentrated to obtain 40 g or crude product. The
crude product was purified by silica gel chromatography to obtain
20.4 g of tetracarboxylic ester (abbreviated to "PENBOM").
[0197] GPC-MS:999 (M+Na).sup.+
(C.sub.49H.sub.68O.sub.20=977.05)
EXAMPLE 14
Synthesis of PECHECHNL
[0198] ##STR49##
[0199] PECHC was synthesized in the same manner as in Example 12.
To a solution consisting of 3.6 g of
2-hydroxy-7-(1-ethylcyclohexyloxy)carbonyl-4-oxytricyclo[4.2.1.03.7]nonan-
-5-one (abbreviated to "ECHNL", described in JP2005-8531-A), 1.6 g
of triethylamine and 20 ml of THF, a solution consisting of 2.2 g
of PECHC and 20 ml of THF was added dropwise. After stirred for two
days, the reaction mixture was diluted with water, and then
extracted with ethyl acetate. The organic layer obtained was washed
with water, dried with anhydrous magnesium sulfate, and then
concentrated. 6.7 g of the crude product obtained was purified by
silica gel column chromatography (developer: hexane/ethyl acetate)
to obtain 4.6 g of tetraester (abbreviated to "PECHECHNL").
[0200] GPC-MS: (PECHECHNL) 1913(m/z).sup.+
(C.sub.105H.sub.140O.sub.32=1914.22)
Polymer Synthesis Example 1
[0201] 2-ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl
methacrylate and 5-methacryloyloxy-2,6-norbornanlactone were
charged in a vessel in molar ratio of 2:1:1 (11.2 g:5.3 g:5.0 g),
and then 50 g of 1,4-dioxane was added thereto to obtain a
solution. To the solution, azobisisobutyronitrile was added in an
amount of 2% by mol to total amount of monomers. The added solution
was heated and stirred at 85.degree. C. for 5 hours. The reaction
mixture was poured into a large quantity of heptane to crystallize.
The crystallization was further repeated twice to obtain 6.3 g of
polymer having weight average molecular weight of 9300. The polymer
is called as Polymer A.
EXAMPLES 15 TO 29 AND COMPARATIVE EXAMPLES 1 TO 2
[0202] The following components were mixed and dissolved, further,
filtrated through a fluorine resin filter having pore diameter of
0.2 .mu.m, to prepare resist liquid.
<Polymer>
10 parts of Polymer A synthesized according to Polymer Synthesis
Example 1 above described in Table 1.
<Acid Generator>
Si: 0.2 part of (4-methylphenyl)diphenylsulfonium
perfluorobutanesulfonate
<Quencher>
Q: 0.0075 part of 2,6-diisopropylaniline
<Solvent>
Y: 51.5 parts of propylene glycol monomethyl ether acetate, 35.0
parts of 2-heptanone and 3.5 parts of .gamma.-butyrolactone
<Supracompound>
0.25 part of Supracompound described in Table 1
[0203] Silicon wafers were each coated with "ARC-29A8", which is an
organic anti-reflective coating composition available from Brewer
Co., and then baked under the conditions: 215.degree. C., 60
seconds, to form a 780 .ANG.-thick organic anti-reflective coating.
Each of the resist liquids prepared as above was spin-coated over
the anti-reflective coating so that the thickness of the resulting
film became 0.25 .mu.m after drying. The silicon wafers thus coated
with the respective resist liquids were each prebaked on a direct
hotplate at 130.degree. C. for 60 seconds. Using an ArF excimer
stepper ("NSR ArF" manufactured by Nikon Corporation, NA=0.55, 2/3
Annular), each wafer thus formed with the respective resist film
was subjected to line and space pattern exposure, with the exposure
quantity being varied stepwise.
[0204] After the exposure, each wafer was subjected to
post-exposure baking on a hotplate at temperature shown in "PEB"
column in Table 1 for 60 seconds and then to puddle development for
60 seconds with an aqueous solution of 2.38 wt %
tetramethylammonium hydroxide.
[0205] Each of a dark field pattern developed on the organic
anti-reflective coating substrate after the development was
observed with a scanning electron microscope, the results of which
are shown in Table 1. The term "dark field pattern", as used
herein, means a pattern obtained by exposure and development
through a reticle comprising chromium base surface (light-shielding
portion) and linear glass layers (light-transmitting portion)
formed in the chromium surface and aligned with each other. Thus,
the dark field pattern is such that, after exposure and
development, resist layer surrounding the line and space pattern
remains on substrate.
Effective Sensitivity:
[0206] It is expressed as the amount of exposure that the line
pattern (light-shielding layer) and the space pattern
(light-transmitting layer) become 1:1 after exposure through 0.13
.mu.m line and space pattern mask and development.
Resolution:
[0207] It is expressed as the minimum size of space pattern which
gave the space pattern split by the line pattern at the exposure
amount of the effective sensitivity.
Line Edge Roughness
[0208] When line edge roughness is very good, its evaluation is
marked by ".largecircle.".
[0209] When line edge roughness is good, its evaluation is marked
by ".DELTA.".
[0210] When line edge roughness is poor, its evaluation is marked
by "X". TABLE-US-00001 TABLE 1 Example PEB Effective Resolu- Line
Edge No. Supracompound (.degree. C.) Sensitivity tion Roughness
Example 15 PECHOM 120 30.5 0.13 .largecircle. Example 16 PECH-AMAD
125 23 0.12 .largecircle. Example 17 PECH-AHAD 125 26 0.12
.largecircle. Example 18 PECH-ANL 125 23 0.12 .largecircle. Example
19 PECH-3-AMAD- 125 26 0.12 .DELTA. ANL Example 20 PECH-2-AMAD- 125
23 0.12 .largecircle. 2-ANL Example 21 GLUCH-5AMAD 125 21.5 0.12
.largecircle. Example 22 GLUCH-4AMAD 125 24.5 0.12 .largecircle.
Example 23 PENB-4AMAD 125 26 0.12 .largecircle. Example 24
PENB-3AMAD 125 24.5 0.12 .largecircle. Example 25 PENB-2-AMAD- 125
29 0.12 .largecircle. 2AHAD Example 26 PENB-2-AMAD- 125 23 0.12
.largecircle. AHAD Example 27 PECH-CHX 120 25 0.12 .largecircle.
Example 28 PENBOM 120 30 0.13 .largecircle. Example 29 PECHECHNL
125 24 0.12 .largecircle. Comparative none 120 32 0.13 X Example 1
Comparative none 125 24.5 0.12 X Example 2
[0211] As is apparent from Table 1, the resists of the Examples 15
to 29 that represent the present composition showed results that
line edge roughness was excellent while presenting equal or higher
sensitivity and resolution compared to the resists of Comparative
Examples 1 and 2.
[0212] The chemically amplified positive resist composition of the
present invention that contains polymer, an acid generator and
Supracompound is excellent in various resist performances such as
sensitivity, and resolution, and particularly in line edge
roughness. Accordingly, this composition is suitable for exposure
with KrF excimer laser, ArF excimer laser, and the like, thereby
providing a resist pattern with a high performance.
* * * * *